Binary and Ternary MetalâOrganic Hybrid Polymers in Aqueous Lead

Subscriber access provided by University of Virginia Libraries & VIVA (Virtual Library of Virginia)

Article

Binary and Ternary Metal-Organic Hybrid Polymers in Aqueous Pb(II)-dicarboxylic acid-(phen) systems. The influence of Oand S-Ligand Heteroatoms on the Assembly of Distinct Lattice Architecture, Dimensionality and Spectroscopic Properties. Catherine Gabriel, Catherine P Raptopoulou, Aris Terzis, Vassilis Psycharis, Marko Bertmer, Farhana Gul-E-Noor, Constantin Mateescu, and Athanasios Salifoglou Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400340y • Publication Date (Web): 29 Apr 2013 Downloaded from http://pubs.acs.org on May 1, 2013

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Binary and Ternary Metal-Organic Hybrid Polymers in Aqueous Pb(II)-dicarboxylic acid-(phen) systems.

The influence of O- and S-Ligand Heteroatoms on the Assembly of Distinct Lattice

Architecture, Dimensionality and Spectroscopic Properties. a

b

b

b

c

c

d

C. Gabriel, C. P. Raptopoulou, A. Terzis, V. Psycharis, F. Gul-E-Noor, M. Bertmer, C. Mateescu, A. a

Salifoglou * a

Department of Chemical Engineering, Laboratory of Inorganic Chemistry, Aristotle University of

Thessaloniki, Thessaloniki 54124, Greece.

b

Institute of Advanced Materials, Physicochemical Processes,

Nanotechnology and Microsystems, Department of Materials Science, NCSR “Demokritos”, Aghia Paraskevi 15310, Attiki, Greece.

c

Faculty of Physics and Earth Sciences, Institute of Experimental

Physics II, Leipzig University, Leipzig 04103, Germany.

d

Banat’s University of Agricultural Sciences and

Veterinary Medicine from Timisoara, Timisoara 300645, Romania.

Abstract Poised to understand the influence of O- and S-heteroatoms on the chemical reactivity of dicarboxylic acids toward Pb(II), leading to crystalline metal-organic hybrid materials with distinct lattice architecture, dimensionality and spectroscopic properties, the synthesis and physicochemical properties of binary/ternary Pb(II)-(O,S)dicarboxylic acid-(phenanthroline) systems was investigated in aqueous media. pH-Specific hydrothermal reactions of Pb(II) with O- and S-dicarboxylic acid ligands and phenanthroline (phen)

afforded

the

variable

dimensionality

metal-organic

Pb(II)

polymers

[Pb3(oda)3]n

(1),

[Pb(phen)(oda)]n (2), [Pb(tda)]n (3), and [Pb(phen)(tda)]n (4). The choice of O- vs. S-ligands in the aqueous systems of Pb(II) and phenanthroline is linked to the emergence of distinct lattice compositiondimensionality (2D-3D) changes at the binary and ternary level, bestowing spectroscopic fingerprint identity to Pb(II)-coordination and luminescence activity.

2D

3D COOH

COOH CH2

3D

Pb(II)

CH2

O

S

CH2

CH2

COOH

2D

COOH

N

N

* Author to whom correspondence should be addressed. Athanasios Salifoglou, Dept. of Chemical Engineering, Laboratory of Inorganic Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece. Tel: +30-2310-996-179 Fax: +30-2310-996-196 E-mail: [email protected]

ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 48

2 Binary and Ternary Metal-Organic Hybrid Polymers in Aqueous Pb(II)-dicarboxylic acid-(phen) systems.

The influence of O- and S-Ligand Heteroatoms on the Assembly of Distinct Lattice

Architecture, Dimensionality and Spectroscopic Properties. a

b

b

b

c

c

d

C. Gabriel, C. P. Raptopoulou, A. Terzis, V. Psycharis, F. Gul-E-Noor, M. Bertmer, C. Mateescu, A. a

Salifoglou * a

Department of Chemical Engineering, Laboratory of Inorganic Chemistry, Aristotle University of

Thessaloniki, Thessaloniki 54124, Greece.

b

Institute of Advanced Materials, Physicochemical Processes,

Nanotechnology and Microsystems, Department of Materials Science, NCSR “Demokritos”, Aghia Paraskevi 15310, Attiki, Greece.

c

Faculty of Physics and Earth Sciences, Institute of Experimental

Physics II, Leipzig University, Leipzig 04103, Germany.

d

Banat’s University of Agricultural Sciences and

Veterinary Medicine from Timisoara, Timisoara 300645, Romania.

Abstract Poised to understand the influence of O -and S-heteroatoms on the chemical reactivity of dicarboxylic acids toward Pb(II), leading to crystalline metal-organic hybrid materials with distinct lattice architecture, dimensionality and spectroscopic properties, the synthesis and physicochemical properties of binary/ternary Pb(II)-(O,S)dicarboxylic acid-(phenanthroline) systems was investigated in aqueous media. pH-Specific hydrothermal reactions of Pb(II) with O- and S-dicarboxylic acid ligands and phenanthroline (phen)

afforded

the

variable

dimensionality

metal-organic

Pb(II)

polymers

[Pb3(oda)3]n

(1),

[Pb(phen)(oda)]n (2), [Pb(tda)]n (3), and [Pb(phen)(tda)]n (4). The choice of O- vs. S-ligands in the aqueous systems of Pb(II) and phenanthroline is linked to the emergence of distinct lattice compositiondimensionality (2D-3D) changes at the binary and ternary level, bestowing spectroscopic fingerprint identity to Pb(II)-coordination and luminescence activity.

* Author to whom correspondence should be addressed. Athanasios Salifoglou, Dept. of Chemical Engineering, Laboratory of Inorganic Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece. Tel: +30-2310-996-179 Fax: +30-2310-996-196 E-mail: [email protected]


Page 3 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


3 Abstract

Poised to understand the influence of O-and S-heteroatoms on the chemical reactivity of dicarboxylic acids toward Pb(II), leading to crystalline metal-organic hybrid materials with distinct lattice architecture, dimensionality and spectroscopic properties, the synthesis and physicochemical properties of binary/ternary Pb(II)-(O,S)dicarboxylic acid-(phenanthroline) systems was investigated in aqueous media. pH-Specific hydrothermal reactions of Pb(II) with O- and S-dicarboxylic acid ligands and phenanthroline (phen) afforded the metal-organic hybrid polymers [Pb3(oda)3]n (1), [Pb(phen)(oda)]n (2), [Pb(tda)]n (3), and [Pb(phen)(tda)]n (4). All materials were characterized by elemental analysis, FT-IR,

13

C&

207

Pb CPMAS

NMR, TGA-DTG, luminescence and single crystal X-ray diffraction. The choice of O- vs. S-ligands in the aqueous systems of Pb(II) and phenanthroline is linked to the emergence of distinct lattice compositiondimensionality (2D-3D) changes at the binary and ternary level, bestowing spectroscopic fingerprint identity to Pb(II)-coordination and luminescence activity. As a result, the interplay between O,S-containing ligands, phenanthroline and Pb(II), a) reveals well-defined contributions of the chemical and structural factors entering the binary and ternary aqueous interactions with Pb(II), and b) clarifies correlations between crystal-lattice architecture and unique physicochemical properties in inorganic-organic Pb(II) materials.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 48

4

Introduction Lead has since long been used in a range of applications including roofing, fuel additives, batteries and solder, and it is often present as a contaminant in the environment. As a heavy toxic metal, it is commonly found in critical life cycles as a result of its widespread use in numerous industrial applications.

1

Thus, its effects on human health are pronounced, with molecular mechanisms of Pb(II) 2

toxicity involving several different types of cellular targets.

In this regard, good knowledge of Pb(II)

chemistry toward variable nature organic substrates, including reactivity involving the lone pair of electrons on the metal ion, coordination number and geometry, is crucial for understanding the toxicity properties of Pb(II).

3

On the other hand, in contrast to transition metals, Pb(II) as a main group metal ion possesses

unique coordination preferences and electronic properties observed rarely in the rest of the periodic table, thereby presenting challenging opportunities to investigate the assembly and synthesis of novel structures 4

of materials with unique physicochemical characteristics.

5

Pursuant to our interest in this area of lead chemistry, efforts were launched to explore the chemical reactivity of low molecular mass ligands a) containing aliphatic dicarboxylic acid groups, and b) heteroatom ether moieties toward Pb(II) in aqueous media. Therefore, O- and S-dicarboxylic acid ligands –

–

of the type O2C-CH2-X-CH2-CO2 , were employed, where X is oxygen or sulfur, specifically exemplified into the diglycolic or oxydiacetic (oda) and thiodiglycolic or thiodiacetic (tda) acid ligands reacting under specific conditions with Pb(II).

The thiodiacetic acid (tda) and oxydiacetic acid (oda) dianions

2–

[X(CH2COO)2] (X = S and O, respectively) emerge as versatile ligands that have been widely explored as multidentate and chelating units toward one or more metals of a different nature. They contain five anchor atoms acting as potential donors, four of which come from two carboxylate groups and one from the thioether or ether functionality. These ligands can promote binding to a single metal in a tridentate fashion, with the two “exo” oxygen donor atoms of the carboxylate groups being capable of additional coordination to another metal or external electrophiles. Such reactivity promotes formation of homo- and hetero-metallic extended crystalline solids, often encompassing stabilizing hydrogen bonds.

The

chemistry of metal-tda complexes is comparatively less developed than that of the related oda congeners. As a matter of fact, the number of X-ray characterized metal derivatives is smaller for tda than for oda derivatives.

6

Cognizant of the paucity of such well-characterized materials and the need to develop rationally justified synthetic routes leading to the synthesis of analogous materials, we report herein the systematic hydrothermal synthesis of a) binary Pb(II)-oda, Pb(II)-tda, and b) ternary Pb(II)-oda-phen, Pb(II)-tda-phen metal-organic hybrid compounds.

Structural and spectroscopic characterization of the new arisen

materials a) reflects the importance of the ligand heteroatom in dictating the type of lattice architecture, dimensionality and physicochemical properties of the synthesized metal-organic hybrid polymers, b) provides the basis of meaningful lattice-dimensionality correlations that justify the variable chemical reactivity of aqueous binary and ternary systems of Pb(II) leading to well-defined crystalline metal-organic hybrid polymers of distinct structural and spectroscopic signature.


Page 5 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


5 Experimental Section Materials and methods. All experiments were carried out under aerobic conditions. Nanopure quality .

water was used for all reactions. Pb(NO3)2, Pb(CH3COO)2 3H2O, diglycolic acid (oda), thiodiglycolic acid (tda), and sodium hydroxide were purchased from Fluka. 1,10-phenanthroline (phen) was supplied by Aldrich. Physical measurements. FT-Infrared spectra were recorded on a Thermo, Nicolet IR 200 FT-infrared spectrometer. Luminescence measurements were carried out on a Hitachi F7000 spectrophotometer. A ThermoFinnigan Flash EA 1112 CHNS elemental analyser was used for the simultaneous determination of carbon, hydrogen, nitrogen, and sulphur (%). The analyser is based on the dynamic flash combustion of the sample (at 1800 °C) followed by reduction, trapping, complete GC separation and detection of the products. The instrument is a) fully-automated and controlled by a PC via the Eager 300 dedicated software, and b) capable of handling solid, liquid or gaseous substances. A TA Instruments thermal analyzer, model Q 600, system was used to run the simultaneous TGA-DTG experiments. The employed heating rate was 5 °C/min. The instrument mass precision was 0.1 µg. About 18.5 mg of sample was placed in an open alumina sample pan for each experiment. High purity helium and air (80/20 in N2/O2) were used at a constant flow rate of 100 mL/min, depending on the conditions required for running the experiment. During the experiment, sample weight loss and rate of sample weight loss were recorded continuously under dynamic conditions, as a function of time or temperature, in the range 30-1000 °C. Prior to activating the heating routine program, the entire system was purged with the appropriate gas for 10 min, at a rate 400 mL/min, to ensure that the desired environment had been established. Solid State NMR spectroscopy. Solid state

13

C CPMAS NMR spectra were obtained on a Varian 400

MHz spectrometer operating at 100.53 MHz. In each case, a sufficient sample quantity was placed in a 3.2 mm rotor. A double resonance HX probe was used. The spinning rate was set at 12 kHz. The RAMP-CP pulse sequence of the VnmrJ library was applied, whereby the

13

C spin-lock amplitude is varied

1

linearly during CP, while the H spin-lock amplitude is kept constant. RAMP-CP eliminates the Hartmann7

Hahn matching profile dependence from the MAS spinning rate and optimizes signal intensity. The solidο

state spectra of 1-4 were recorded with 300-1000 scans, using a 90 pulse width of 5.0 µs for 1, 5.6 µs for 2, 3.3 µs for 3, and 4.5 µs for 4, a contact pulse of 2.8 ms for 1, 4.0 ms for 2, 2.8 ms for 3, and 2.0 ms for 4, and a recycle delay of 10 s for 1-4. The adamantane (C10H16) CH group was used as an external reference (38.54 ppm) to report the chemical shifts of

13

C resonance peaks. The recorded spectra were

consistent with coordination of oda, tda and phen to the Pb(II) ion. The

207

Pb CPMAS NMR spectra for compounds 1 and 2 were obtained on a Bruker Avance 750 1

spectrometer at a frequency of 156.71 MHz using a simple one-pulse sequence without H decoupling. The

207

Pb 90° pulse length was 2.75 µs and the recycle delays 30 s for 1 and 300 s for 2, with spinning

frequencies of 8.3 and 8.7 kHz, respectively. For the high resolution solid state natural abundance

207

Pb

NMR spectra of compounds 3 and 4, a Bruker Avance 400 NMR spectrometer at a frequency of 83.67



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 48

6 1

MHz was employed. decoupling. The 90

o 1

In this case, cross-polarization from protons was used with high power H H pulse was 3 µs and the contact time 2 ms for both 3 and 4. For 3, 6142 scans

and for 4 6820 scans were accumulated, respectively. The recycle delays were 15 s for 3 and 18 s for 4. The spinning rate was 7.3 kHz in both cases.

To identify the isotropic chemical shifts in all cases,

measurements with different spinning frequencies were used. All measurements were performed at room temperature. Referencing was done with Pb(NO3)2 as a secondary reference with a resonance at -3473.5 8

9

ppm with respect to PbMe4. Analysis was done with the dmfit program. The results of the chemical shift anisotropy tensor are given according to the Haeberlen notation,

10

with the terms anisotropy ∆σ and

asymmetry η defined as ∆σ = δzz – δiso and η = (δyy – δxx)/(δzz – δiso), with the principal components of the tensor being |δzz-δiso| ≥ |δxx-δiso| ≥ |δyy-δiso]. Preparation of [Pb3(oda)3]n (1).(Method a) A quantity of Pb(ΝΟ3)2 (0.33 g, 1.0 mmol) was placed in a flask and dissolved in 10 mL of H2O. Subsequently, oda (0.27 g, 2.0 mmol) was added to the reaction flask slowly and under continuous stirring. To the resulting reaction mixture, phen (0.20 g, 1.0 mmol) was added under stirring. Finally, a sodium hydroxide solution was added slowly to adjust the pH to a final value of ~3. The resulting reaction mixture was allowed to stir for an additional ½ h. Then, it was placed o

in a 23 mL Teflon-lined stainless steel reactor and heated to 160 C for 85 h. Subsequently, the reactor was allowed to cool to room temperature.

At the bottom of the Teflon-lined stainless steel reactor

container appeared crystals. They (0.17 g, ~46 %) were collected by filtration, washed with water and airdried. Anal. Calcd for 1, [Pb3(oda)3]n (1) (C12H12O15Pb3, Mr 1017.79): C 14.16%, H 1.19%. Found: C 14.20%, H 1.18%. .

(Method b) A quantity of Pb(CH3COO)2 3H2O (0.20 g, 0.54 mmol) was placed in a flask and dissolved in 10 mL of H2O. Subsequently, oda (0.14 g, 1.08 mmol) was added slowly and under continuous stirring. The final pH value of the resulting solution was ~3. The reaction mixture was allowed to stir for ½ h. o

Then, it was placed in a 23 mL Teflon-lined stainless steel reactor and heated to 160 C for 85 h. Subsequently, the reactor was allowed to cool to room temperature. The resulting solution was left for slow evaporation and a few days later colorless crystals appeared at the bottom of the container. The resulting crystals (0.070 g, 20%) were collected by filtration, washed with water and air-dried. Anal. Calcd for 1, [Pb3(oda)3]n (1) (C12H12O15Pb3, Mr 1017.79): C 14.16%, H 1.19%. Found: C 14.18%, H 1.20%. .

Preparation of [Pb(phen)(oda)]n (2). A quantity of Pb(CH3COO)2 3H2O (0.20 g, 0.54 mmol) was placed in a flask and dissolved in 10 mL of H2O. Subsequently, oda (0.14 g, 1.08 mmol) was added slowly and under continuous stirring. In the emerging reaction mixture, phen (0.11 g, 0.54mmol) was added under stirring. Finally, a solution of sodium hydroxide was added slowly to adjust the pH to a final value of ~8. The resulting reaction mixture was allowed to stir for an additional ½ h and then placed in a 23 mL Teflono

lined stainless steel reactor and heated to 160 C for 85 h. Subsequently, the reactor was allowed to cool to room temperature. The resulting solution was left for slow evaporation and a few days later colorless


Page 7 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


7 crystals appeared at the bottom of the container. The crystals (0.40 g, 13 %) were collected by filtration, washed with water and air-dried. Anal. Calcd for 2, [Pb(phen)(oda)]n (2) (C16H12O5Ν2Pb, Mr 519.47): C 36.99%, H 2.33%, Ν 5.39%. Found: C 36.70%, H 2.30%, N 5.29%. .

Preparation of [Pb(tda)]n (3). A quantity of Pb(CH3COO)2 3H2O (0.37 g, 1.0 mmol) was placed in a flask and dissolved in 10 mL of H2O. Subsequently, tda (0.30 g, 2.0 mmol) was added slowly and under continuous stirring. The final pH value of the resulting solution was ~3. The reaction mixture was allowed o

to stir for ½ h. Then, it was placed in a 23 mL Teflon-lined stainless steel reactor and heated to 160 C for 85 h. Subsequently, the reactor was allowed to cool to room temperature. At the bottom of the Teflonlined container grayish crystals appeared. The resulting crystals (0.17 g, 48%) were collected by filtration, washed with water and air-dried. Anal. Calcd for 3, [Pb(tda)]n (3) (C4H4O4SPb, Mr 355.32): C 13.52%, H 1.13%, S 9.02%. Found: C 13.48%, H 1.15%, S 8.97%. .

Preparation of [Pb(phen)(tda)]n (4). A quantity of Pb(CH3COO)2 3H2O (0.37 g, 1.0 mmol) was placed in a flask and dissolved in 10 mL of H2O. Subsequently, tda (0.30 g, 2.0 mmol) was added slowly and under continuous stirring. Then, phen was added (0.20 g, 1.0 mmol) under stirring. Finally, a solution of sodium hydroxide was added slowly to adjust the pH to a final value of ~4. The resulting reaction mixture was allowed to stir for ½ h. Then, it was placed in a 23 mL Teflon-lined stainless steel reactor and heated to o

160 C for 85 h. Subsequently, the reactor was allowed to cool to room temperature. At the bottom of the Teflon-lined container appeared crystals. The resulting crystals (0.13 g, 25 %) were collected by filtration, washed with water and air-dried. Anal. Calcd for 4, [Pb(phen)(tda)]n (4) (C16H12O4Ν2SPb, Mr 535.55): C 35.88%, H 2.26%, Ν 5.23%, S 5.99%. Found: C 35.85%, H 2.22%, Ν 5.27%, S 5.95%. X-ray crystal structure determination.

X-ray quality crystals of compounds 1-4 were grown from

aqueous solutions subjected to hydrothermal reactivity conditions. Single crystals, with dimensions 0.27 x 0.27 x 0.64 mm (1), 0.17 x 0.22 x 0.45 mm (2), 0.15 x 0.17 x 0.62 mm (3), and 0.07 x 0.25 x 0.34 mm (4) were mounted on glass fibers. The data collection for 1 was carried out at room temperature. The o

crystals of 2, 3 and 4 were taken from the mother liquor, and cooled to -93 C by placing them immediately into a nitrogen-cold stream on the diffractometer goniometer for data collection. Diffraction measurements were made on a Rigaku R-AXIS SPIDER Image Plate diffractometer using graphite monochromated Mo Kα radiation.

Data collection (ω-scans) and processing (cell refinement, data reduction, and

empirical/numerical absorption correction) were carried out using the CrystalClear program package.

11

Crystallographic details are given in Table 1. The structures of compounds 1-4 were solved by direct methods using SHELXS-97, 97.

12

2

and refined by full-matrix least-squares techniques on F with SHELXL-

13

All non-H atoms were refined anisotropically. Hydrogen atoms were either located by difference maps and refined isotropically or introduced at calculated positions as riding on bonded atoms. Plots of all structures were drawn using the Diamond 3.1 crystallographic package.


14


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 48

8 Results and Discussion Synthesis. The hydrothermal synthesis of the colorless compound 1 was pursued through a reaction in the ternary system involving Pb(NO3)2, oda acid and phen (or in the absence of phen) in water at pH~3. The stoichiometric reaction leading to the formation of 1 is shown below (Reaction 1):

COOH CH2 3n Pb(NO3)2 +

3n

N

O

+

pH 3

6n N

CH2 COOH (phen)

[Pb3(C4H4O5)3]n

Compound 1 was previously reported

15

+

6n phenH+NO3-

as arising from a different synthetic procedure, with its

structural report accompanied by limited spectroscopic characterization (IR and TGA). In this case, a detailed report of the straightforward synthesis of 1 is linked to a detailed presentation of the crystal structure of 1, further supported by an arsenal of spectroscopic techniques. Consequently, a basis is provided for direct comparison of the a) lattice architecture and dimensionality between binary 1 and its related ternary congener 2, and b) chemical reactivity of the two systems (binary and ternary) out of which 1 and 2 arise. In a similar reaction, Pb(CH3COO)2 and oda reacted in water with phen and sodium hydroxide at pH~8 and led to compound 2. The stoichiometric reaction leading to the formation of 2 is shown below (Reaction 2):


Page 9 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


9

COOH CH2 n Pb(CH3COO)2 +

n

N

O

pH 8

n

+

+ 2n NaOH N

CH2 COOH

[Pb(C4H4O5)(phen)]n + 2n CH3COONa + 2n H2O

Compound 3 emerges from the reaction of Pb(CH3COO)2 and tda in water at pH~3. The stoichiometric reaction leading to the formation of grayish 3 is shown below (Reaction 3): COOH CH2 n

n Pb(CH3COO)2 +

pH 3 [Pb(C4H4O4S)]n + 2n CH3COOH

S CH2 COOH

In a similar reaction, Pb(CH3COO)2 and tda reacted in water in the presence of phen at pH~4, ultimately leading to the isolation of compound 4. The stoichiometric reaction affording gray 4 is shown below (Reaction 4):

COOH CH2 n Pb(CH3COO)2 +

n

S CH2

N +

n pH 4 N

COOH

[Pb(phen)(C4H4O4S)]n + 2n CH3COOH



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 48

10 II

II

The derived binary Pb -oda and Pb -tda materials and their ternary congeners with phen were easily retrieved from the reaction mixtures in pure crystalline form via hydrothermal synthesis.

Elemental

analysis of the isolated crystalline products projected the molecular formulation [Pb3(oda)3] (1), [Pb(phen)(oda)] (2), [Pb(tda)] (3), and [Pb(phen)(tda)] (4), respectively. Further spectroscopic evaluation of the crystalline products by FT-IR confirmed the presence of the respective ligands being bound to Pb(II), thereby conforming to the proposed formulations. Finally, X-ray crystallography confirmed the analytical and spectroscopic results by rendering the molecular formulation of the crystalline products in all four cases. Further chemical reactivity under variable reaction conditions leading to new Pb(II) species of oda and tda are currently being investigated. Compounds 1- 4 are insoluble in water. All four compounds are stable in the crystalline form in the air at room temperature for long periods of time. Description of crystallographic structures. Compound 1 crystallizes in the triclinic crystal space group Pī with two molecules in the unit cell. The molecular structure of 1 reveals a 3D coordination polymer. The monomeric unit consists of three Pb(II) metal ions, and three oda ligands (Figure 1A). Pb(1) is bound to six carboxylato oxygen atoms from four different oda (-2) ligands and one ether oxygen atom from one of the oda (-2) ligands. As a result, the coordination number around Pb(1) is seven (Figure 1A) and the polyhedron formed by the seven oxygen atoms could be described as consisting of one slightly distorted tetragonal base with a triangle at an antiprismatic position (Figure 1A, inset). Pb(2) exhibits the same coordination number, seven, formulated by carboxylato oxygen atoms from four different oda (-2) ligands and one ether oxygen atom from one of the oda (-2) ligands (Figure 1B), which form a polyhedron much like the one surrounding Pb(1) (Figure 1B, inset). Pb(3) exhibits a coordination number nine, formulated by carboxylato oxygen atoms from five different oda (-2) ligands and one ether oxygen atom from one of the oda (-2) ligands (Figure 1C). The polyhedron formed by the oxygen atoms surrounding Pb(3) could be described as a pentagonal pyramid, with the pentagonal face capped with a triangle (Figure 1C, inset). Thus, Pb(1), Pb(2) present an O7 coordination environment and Pb(3) presents an O9 coordination environment, respectively (Table 2). The three crystallographically independent oda(-2) ligands adopt two different coordination modes (Figure 1A) upon binding to the three Pb(II) metal ion centers (Scheme 1); specifically, the oda (-2) ligands defined by oxygen atoms O(1)-O(5) and O(21)-O(25) adopt the µ52

2

2

κ O:κ O':κ O'':κO''':κO'''' coordination mode and the ligand defined by oxygen atoms O(11)-O(15) adopts 2

2

the µ3-κ O:κ O':κO'':κO''':κO'''' mode. Each ligand a) behaves as a tridentate chelator around one Pb(II) ion through the ether oxygen atom and two carboxylato oxygens from different carboxylato moieties, and b) uses its two carboxylato groups to further bind four (µ5-mode) or two (µ3-mode) metal ions. The µ5-oda (-2) ligand, defined by oxygen atoms O(1)-O(5), bridges two Pb(1) ions, one Pb(2) and two Pb(3) ions, …

…

…

with the closest Pb Pb interatomic distances being Pb(3) Pb(3)** = 4.225(2) Å, Pb(1) Pb(1)’ = 4.366 Å, …

…

Pb(2) Pb(1)’ = 4.704(2) Å, and Pb(1) Pb(3) = 5.224(4) Å. The µ5-oda (-2) ligand, defined by oxygen …

atoms O(21)-O(25), bridges one Pb(1) ion, two Pb(2) and two Pb(3) ions with the closest Pb Pb …

…

interatomic distances being Pb(3)!!!…Pb(3)*** = 4.201(2) Å, Pb(2)!! Pb(2)’’’’= 4.307(1) Å, Pb(1) Pb(2)’’’’ = …

4.969(2) Å, and Pb(2)!! Pb(3)!!! = 5.044(1) Å. The µ3-oda (-2) ligand, defined by oxygen atoms O(11)-


Page 11 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


11 …

O(15), bridges one Pb(1), one Pb(2) and one Pb(3) ions with the closest Pb Pb interatomic distances …

…

being Pb(1) Pb(3)* = 4.553(3) Å, and Pb(3)* Pb(2)&= 4.771(3) Å. Symmetry operations: ('): -x, 1-y, 1-z; (''''): 1-x, 1-y, 1-z ; (*): -x, -y, -z; (**):1-x, -y, -z; (***): -x, -y, 1-z; (!!): -x,1-y,1-z; ( !!!): -x,y,1+z ; (&):-1+x,1+y,-1+z The backbone of the architecture in the structure of 1 is the polyhedra around the Pb(3) atoms (Figure 1D, blue polyhedra). These polyhedra extent along the a crystallographic axis in a zig-zag fashion by sharing the edges O(5)-O(5)**, and O(25)***-O(25)**** [Symmetry operations: (**):1-x, -y, -z; (***): -x, y, 1-z; (****): x, y, -1+z]. Pairs of edge-sharing Pb(1) and Pb(2) polyhedra are attached to these chains in an alternating way though the corners (oxygen atoms) of O(11), O(4) and O(15), O(24), respectively. Pb(1) pairs of polyhedra share edges formed by O(1), O(1)’ atoms, and those of Pb(2) pairs share edges formed by O(22)’’, O(22)’’’’ [Symmetry operations: ( '): -x, 1-y, 1-z; (''): x, 1+y, z;, 1+z; (''''): 1-x, 1-y, 1-z]. The Pb(1) and Pb(2) pairs of polyhedra serve as pillars of Pb(3) chains; those of the first along the [011] (Figure-1E) diagonal direction and those of the second along the [001] (Figure 1E) crystallographic direction. Figure-1E shows the development of links for the chains formed by Pb(3) along the [001] and [011] crystallographic directions, while Figure 1E shows the 3D lattice architecture of structure in 1. The two different oda(-2) coordination modes create three kinds of macrometallocycles. One of them is a 24membered macrometallocycle (Figure 2A) comprised by four Pb(1) ions, two Pb(3) ions, two oda ligands, and four carboxylato oxygen atoms from abutting ligands.

The second one is a 28-membered

macrometallocycle (Figure 2B) composed of two Pb(1) ions, two Pb(2) ions, one Pb(3) ion, three oda ligands and two carboxylato oxygen atoms from abutting ligands. The third type of macrometallocycle (Figure 2C) contains only Pb(II) ions and oxygen atoms.

Specifically, the 24-membered

macrometallocycle is assembled by four Pb(1) ions, four Pb(2) ions, four Pb(3) ions and 12 carboxylato oxygen atoms from the oda ligands.

The three types of macrometallocycles are integrated into the

collective lattice of 1 (Figure 2D). Compound 2 crystallizes in the monoclinic space group C2/c with four molecules in the unit cell. The molecular lattice structure of 2 reveals a 2D coordination polymer. The monomeric unit consists of one Pb(II) metal ion, one phen, and one oda(-2) ligand. The Pb(II) ion sits on a two-fold axis of symmetry, …

…

also passing through the middle of the C5 C5 and C6 C6 bond of phen. The oda(-2) ligand sits on another two-fold axis of symmetry passing through the ether oxygen atom. Each Pb(II) ion, is eightcoordinate and bound to the two nitrogen atoms of the phen ligand and to six carboxylato oxygen atoms from four oda(-2) ligands (Figure 3A, Table 3).

2

2

The oda ligand exhibits a µ4-κ O:κ O':κO'':κO'''

coordination mode utilizing its two carboxylato moieties to bridge four symmetry related Pb(II) ions (Scheme 1, Figure 3A).

…

The observed Pb Pb interatomic distances due to bridging through the µ4-

ligands are Pb···Pb* = 10.253(2) Å [(*): 1+x, y, z]. Two Pb(II) atoms are linked by two symmetrically equivalent O(12) atoms [O(12) and O(12)’], forming planar four-membered rings Pb-O(12)-Pb’-O(12’), with interatomic distances Pb···Pb’ = 4.486(1) Å [('): -x, -y, 1-z]. Although O(12)-O(12)’ could be considered as an edge shared by neighboring eight-cornered polyhedra surrounding Pb(II) ions, the polyhedral



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 48

12 description of the structural architecture is not very helpful because of the high distortion of the Pb(II) polyhedron. The basis of the structural architecture in 2 is the two different bonding modes of the oda ligand, described above. Pb(II) centers, which take part in the planar four-membered rings, form chains along the c crystallographic axis and these chains are linked through the µ4-coordinated mode of the oda ligands along the a crystallographic axis (Figure 3B). The oda ligand through the two bonding modes with the Pb(II) ions builds a 2D polymer, which extents parallel to the ac crystallographic plane (Figure 3B). The planar four-membered rings can be alternatively described as dinuclear units containing a Pb2O2 core, which is very common in Pb(II)-O compounds. The dihedral angle between neighboring Pb2O2 cores is o

49.9 .

The dinuclear units are linked through two different oda (-2) ligands and form 16-membered

macrometallocycles. The presence of weak π-π interactions between the aromatic rings of the phen molecules contributes to the stability of the overall crystal structure (Figure 3C). The mean planes of the phen molecules belonging to different 2D layers are parallel to each other and the average distance between the mean planes is 3.449(8) Å.

The oda (-2) ligand displays different coordination modes

between 1 and 2. In the case of 1, Pb(II) ions are coordinated through the carboxylato oxygen atoms and through the ether oxygen atom.

In the case of 2, the Pb(II) ions are coordinated only through the

carboxylato oxygen atoms, with the ether oxygen atoms not participating in the coordination sphere of Pb(II). Moreover, the carboxylato moieties in 2 adopt only one of the coordination modes found in 1. Compound 3 crystallizes in the orthorhombic space group Iba2, with eight molecules in the unit cell. The molecular structure of 3, reveals a 2D coordination polymer [Pb(tda)]n. The monomeric unit consists of one Pb(II) metal ion, and one tda (-2) ligand in the lattice asymmetric unit. The Pb(II) metal ion is seven-coordinate and bound to the sulfur atom of the tda (-2) ligand and to six carboxylato oxygen atoms from four tda (-2) ligands (Figure 4A, Table 4). The tda (-2) ligands coordinated to the Pb(II) ions 2

2

all have the same coordination mode µ4-κ O:κ O':κS:κO'':κO''' (Scheme 1).

The closest Pb···Pb

interatomic distances are Pb*···Pb** = 4.344(1) Å through the carboxylato atom O(1) of the tda (-2) ligand. …

2

2

…

The Pb Pb interatomic distance through the µ4-κ O:κ O':κS:κO'':κO''' ligand is 4.913(1) Å for Pb Pb*** [symmetry operations: (*): 0.5-x, -0.5+y, z; (**): x, -y, 0.5+z; (***): x, 1-y, 0.5+z]. All neighboring Pb(II) centers share single carboxylato oxygen atoms of the tda (-2) ligand and this type of coordination leads to a 2D network, which extents parallel to the (001) crystallographic plane (Figure 4B). Compound 4 crystallizes in the triclinic space group Pī, with two molecules in the unit cell. The molecular lattice structure of 4 reveals a 1D coordination polymer. The asymmetric unit contains one Pb(II) ion, one phen molecule, and one tda (-2) ligand. The repeating unit of the 1D coordination polymer consists of a centrosymmetric dimer [Pb2(phen)2(tda)2]. Each Pb(II) ion, is six-coordinate, and bound to the two nitrogen atoms of the phen molecule and to four carboxylato oxygen atoms from three tda(-2) ligands (Figure 5A, Table 5). The tda (-2) ligands coordinated to the Pb(II) ions all have the same coordination mode µ3-κO:κO':κO'':κO''' (Scheme 1). The closet Pb···Pb interatomic distance within the …

dimer is Pb···Pb’ = 3.597(1) Å [('): 1-x, 1-y, -z], whereas the corresponding Pb Pb distance through the µ3-


Page 13 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


13 …

κO:κO':κO'':κO''' tda(-2) ligand is 8.774(1) Å for Pb Pb* [(*):x,-1+y,z], i.e. the length of the b-axis. Therefore, the chains in the lattice of 4 extend parallel to the crystallographic b axis (Figure 5A). The interesting feature here is the fact that on one end of the tda (-2) ligands the two carboxylato oxygen atoms are coordinated to the same Pb(II) metal ion, while on the other end the two carboxylato oxygen atoms are coordinated to two different Pb(II) metal ions.

As a result of coordination, two kinds of

macrometallocycles form (Figure 5A). One of them is a 8-membered macrometallocycle, consisting of two Pb(II) ions, two carbon atoms and four carboxylato oxygen atoms (Pb-O(23**)-C(24**)-O(24**)-Pb'’-O(23')C(24')-O(24')) (Figure 5A). The second one is a 16-membered macrometallocycle, consisting of two Pb(II) ions and part of two tda (-2) ligands [Pb-O(21)-C(21)-C(22)-S-C(23)-C(24)-O(24)-Pb’-O(21’)-C(21’)-C(22’)S’-C(23’)-C(24’)-O(24’)]. The phen ligands belonging to neighboring chains are parallel to each other and participate in weak π-π stacking interactions, which contribute to the stability of a 2D network parallel to the (100) plane (Figure 5B). The average distance between the mean planes is 3.373 Å. The Pb-O bond distances in 1-4 are quite similar and analogous to those observed in other .

compounds, such as Pb4(C4H4O5)3(NO3) H2O (2.464(13)-2.890(13) Ǻ), 2.91(2) Ǻ),

17

5

[Pb(phen)(Heida)]·4H2O (2.454(6)-2.699(6) Ǻ),

[Pb(NNO)(FA)0.5] (2.483(8)-2.586(8) Ǻ), .

20

acid), {[Pb2(fum)2(H2O)4] 2H2O}n (2.517(5)-2.858(5) Ǻ), (2.44(1)-2.91(1) Ǻ),

21

19

.

5

[Pb(C12H8N2)(C4H2O4)] 2H2O

18

[Pb3(NO3)(Dpot)]n (2.379(6)-

[Pb2(C12H8N2)(C4H2O4)2] (2.439(3)-2.853(3) Ǻ),

(2.454(5)-2.656(5) Ǻ),

2.847(1) Ǻ).

.

[Pb2(C12H8N2)4(C4H2O4)](NO3)2 (2.538(3)-2.624(3) Ǻ), [Pb2(C12H8N2)4(CO3)(C4H2O4)] 6H2O 5

2.880(6) Ǻ),

[Pb(C4H4O5)(H2O)] (2.490(3)-

5

(2.451(5)-2.872(7) Ǻ), 17

16

(NNO = Nicotinic acid N-Oxide, FA = fumaric 18

[Pb(fum)]n (2.399(5)-2.811(5) Ǻ),

Pb2(phen)4(C4H4O4)(NO3)2 (2.490(3)-2.638(3) Ǻ),

22

[Pb(C4H4O4)]

and [Pb(C6H6O7)]n (2.397(7)-

23

Several compounds, also, exist in the literature containing different metal ions coordinated to oda 24,25,26,27,28,29

and tda

30,31,32,33

ligands. Tables 6 and 7, list terminal M-O and metal–ether atom (M-O or M-

S) bond distances for oda and tda metal-bound ligands in both binary and ternary M-oda/tda compounds, including 1-4. FT-IR spectroscopy. The FT-Infrared spectrum of 1-4 in KBr revealed the presence of vibrationally active carboxylate groups. Antisymmetric as well as symmetric vibrations for the carboxylate groups of the coordinated ligands were present.

–

Specifically, antisymmetric stretching vibrations νas(COO ) for the -1

-1

-1

carboxylate carbonyls appeared in the range 1592-1550 cm (1), 1597-1518 cm (2), 1559 cm for (3), -1

–

and 1583-1511 cm for (4). Symmetric vibrations νs(COO ) for the same groups appeared in the range -1

-1

-1

-1

1433-1350 cm (1), 1404 cm (2), 1395-1366 cm (3), and 1388-1359 cm (4). The frequencies of the observed carbonyl vibrations were shifted to lower values in comparison to the corresponding vibrations in free oda and tda, indicating changes in the vibrational status of the ligands upon binding to the Pb(II) ion. Confirmation of this connection came through the X-ray crystal structures of 1-4. NMR spectroscopy. The

13

C spectrum of 1 (Figure 6) exhibits one resonance at 73.6 ppm, attributed to

the methylene carbons in the oda ligand, and one resonance at 181.5 ppm for the oda carboxylate carbons. Preferably, due to bonding to the Pb(II) ion, they are shifted to lower field compared to free carboxylic carbons.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 48

14 The spectrum of 2 (Figure 7) exhibits similar peaks with 1 at 75.7 ppm for the methylene carbons of the oda ligand and 180.2 ppm for the oda carboxylate carbons bound to the Pb(II) ion. In addition, there are several signals between 123.9 and 150.4 ppm, in agreement with the presence of the phen molecule in the coordination sphere of Pb(II). The spectrum of 3 (Figure 8) shows similar features as 1, with signals at 44.2 ppm for the methylene carbons and 181.2 ppm for the tda carboxylate carbons. The effect of the sulphur vs. oxygen in tda vs. oda ligands is clearly visible by the high-field shift of the methylene carbon signals by about 30 ppm. Finally, Figure 9 shows the spectrum of 4 with resonances at 44.7 ppm for the methylene carbons of the tda ligand and 182.2 ppm for the tda carboxylate carbons. The range from 118.1-152.3 ppm is – as also seen for 2 - due to the signals from the phen ligand. All resonances lie in lower fields compared to the free ligands.

The aforementioned observations are consistent with the structural composition of all

compounds investigated and confirmed by X-ray crystallography. The

207

Pb nucleus has a spin of 1/2, a fact that has been reportedly exploited to gain insight into the

structural features of Pb(II) compounds.

34,35,36,37,38

Typically, Pb(II) NMR signals show strong chemical

shift anisotropies leading to a multitude of spinning sidebands in MAS experiments. The identity of the main resonance in each case is, therefore, confirmed by running experiments with different spinning frequencies; those resonances, whose chemical shift does not change with frequency, are the main resonances, with the rest of them being spinning sidebands. Figures 10-13 represent the

207

Pb NMR

spectra of 1 to 4, respectively. In case of compound 1 there are three different chemical shifts for the three different Pb(II) ions (-2232 ppm for Pb(1), -2330 ppm for Pb(2) and -2873 ppm for Pb(3)). In the other three cases, almost identical isotropic chemical shifts are observed (-1970 ppm for 2, –1924.7 ppm for 3 and –1925.1 ppm for 4). For compound 1, three different species are observed in agreement with the crystal structure, the isotropic chemical shifts of which are -2232, -2330, and -2873 ppm.

For

compounds 2, 3, and 4, one signal is observed for each species, also in agreement with the crystal structure. The isotropic chemical shifts of the three compounds are very similar: -1970 ppm for 2, –1924.7 ppm for 3, and –1925.1 ppm for 4. There is no direct assignment of chemical shift ranges (for

207

Pb, shift

ranges of more than 10,000 ppm have been reported) to certain metal coordination numbers.

The

coordinating atom also plays a significant role. For the Pb(3) ion in compound 1, however, an assignment to the -2873 ppm signal is possible because of the large difference in chemical shift compared to the other signals as well as the smaller anisotropy. The anisotropy parameter ∆σ of this signal is only -17.8 kHz (η=0.40) compared to all other signals having anisotropies of 42.0 kHz (η=0.70) and -64.0 kHz (η=0.45) for 1, -90.0 kHz (η=0.40) for 2, -58.1 kHz (η=0.40) for 3, and -59.1 kHz (η=0.35) for 4. Anisotropy and asymmetry reflect the symmetry of the surroundings of the Pb(II) center and combine effects of bonding distances, angles and coordinating atom. The

207

Pb chemical (isotropic and anisotropic) shifts are very

sensitive to the electronic structure of Pb(II), suggesting that the coordination number and symmetry are not the only contributors to the observed chemical shifts. Further conclusions, however, would require density functional theory calculations of the chemical shifts, a feat which is outside the scope of the current manuscript. It should, also, be noted that the signals of compound 1 show a slight variation of


Page 15 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


15 isotropic chemical shifts with spinning frequency (less than 20 ppm between 0 and 10 kHz).

This

observation is not uncommon and is related to a slight heating of the sample due to sample rotation. For analysis, the isotropic chemical shifts were compared at three spinning speeds and the given shifts are the 2

result of a linear extrapolation to a spinning frequency of 0 Hz. The linear regression had an R value of above 98% in all three cases. Thermal studies. The thermal decomposition of 1-4 was studied by TGA-DTG under an atmosphere of oxygen. 1 is thermally stable up to 205 °C (in line with past reports),

15

whereas 2 is thermally stable up to

250 °C (Figure 14). From that point on, there are two consecutive process steps between 205 and 400 °C for 1, and two consecutive steps between 250 and 445 °C for 2, respectively, both involving decomposition of the organic part of the materials in question. No clear plateaus are reached in these stages, suggesting that the derived products are unstable and decompose further. Mass loss calculations show that the ﬁnal decomposition product is PbO for compounds 1 and 2. Decomposition is complete at 400 °C for 1 and 445 for 2 °C, with the total mass loss being 81.8% (calcd 78.1%) and 58.6% (calcd 57.0%), respectively. The DTG profiles of both 1 and 2 exhibit clear features that correspond to the aforementioned TGA processes. Compound 3 is thermally stable up to 250 °C, whereas 4, is thermally stable up to 207 °C. From that point on, there is a one process step between 210 and 377 °C for 3 and two consecutive steps between 230 and 444 °C for 4, respectively, involving decomposition of the organic part of the title compounds. No clear plateaus are reached in these stages, suggesting that the derived products are unstable and decompose further.

Mass loss calculations show that the ﬁnal decomposition product is PbO for

compound 3 and 4. Decomposition is complete at 377 °C for 3 and 447 for 4 °C and the total mass loss is 38.0% (calcd 37.0%) and 56.4% (calcd 58.0%), respectively. The DTG profiles of both compounds exhibit clear features that correspond to the aforementioned TGA processes. Luminescence. Functional metal–organic frameworks based upon d

10

configuration have been studied

for their photoluminescence properties and several potential applications.

39,40,41

The solid-state

photoluminescence spectra of 1-4 along with oda, tda and phen ligands have been studied at room temperature (Figure 15 A-B, Supporting Information). The results at hand suggest that free oda does not possess any luminescence at room temperature. In the case of the free tda ligand, the main emission bands emerge at 450 nm and 469 nm (λex 300 nm), which could be attributed to the π*― n transitions. The strongest emission band for the free phen ligand appears at 417 nm (λex 368 nm) and could attributed to the π*― π transitions. The emission spectrum of 1 shows two strong peaks at 497 nm and 536 nm (λex 335 nm), while 2 exhibits a strong band at 574 nm (λex 363 nm). The observed features in 1 and 2 could be tentatively assigned to ligand-to-metal-charge-transfer (LMCT) processes, with additional contribution from interligand fluorescence in the case of the ternary compound 2 (vide infra).

42,43

These observations

suggest that coordination polymers 1 and 2 could be considered as potential fluorescent porous materials.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 48

16 The emission spectra of 3 and 4 were similar to each other and to the free ligand, exhibiting two emission bands at 450 nm and 469 nm (λex at 300 nm) with no shift. Discussion Chemical reactivity in Pb(II)-(O,S)dicarboxylic acid-phen systems vs. structural speciation. Poised to delineate the factors influencing the assembly of hybrid binary and ternary Pb(II)-carboxylato lattice architectures of defined dimensionality, due attention was focused on key O- and S-heteroatom containing dicarboxylic acids and their physicochemical characteristics. Thus, in the present work, the aqueous synthetic chemistry of Pb(II) with two different, yet structurally congener, (O,S)-dicarboxylic acids was investigated under hydrothermal conditions. Oda was employed in the study aiming at a comprehensive structural speciation in a binary system with Pb(II), followed by an extension of the observed chemical reactivity into a ternary system encompassing the aromatic chelator phenanthroline. The hydrothermal synthesis led to the isolation of a new metal-organic hybrid polymer [Pb3(oda)3]n (1), the repeating unit of which was a trinuclear Pb(II)-oda assembly. Concomitantly, the synthetic investigation of the ternary system of Pb(II)-oda-phen led to another metal-organic hybrid polymer [Pb(phen)(oda)]n (2), containing a ternary mononuclear assembly. On the other hand, the investigation of the binary system Pb(II)-tda led to the isolation of the metal-organic hybrid polymer [Pb(tda)]n (3) containing a mononuclear Pb-tda assembly. Delving into the ternary system of Pb(II)-tda-phen led to the corresponding metal-organic hybrid polymer [Pb(phen)(tda)]n (4) exhibiting unique lattice features (Scheme 2). Undoubtedly, phen, as a ternary ligand, induces profound lattice changes in the materials arising through both dicarboxylic acids reacting with Pb(II). The structural differentiation of the arising lattices between 1 and 2 is a result of the presence of the phen ligand, coordinated to Pb(II) in a bidentate fashion. There is an obvious differentiation in the chemical reactivity between the O- and S-containing dicarboxylic acids toward Pb(II) at the binary level, ultimately leading to the differentiation of the molecular assembly and lattice architecture between 1 and 2. In 1, there are two types of Pb(II) ions bearing different coordination numbers. Pb(1) and Pb(2) are seven coordinate, whereas Pb(3) is nine coordinate, with all coordination sites taken up by O terminals belonging to oda ligands. Both carboxylate oxygen atoms and ether oxygen atoms participate in the coordination sphere of both types of Pb(II) ions. With respect to the dicarboxylic acid, oda is coordinated to Pb(II) through two different modes of binding as shown in Scheme 1. These coordination modes may influence the final packing of the crystal lattice in 1 and the associated architecture presented in Figure 2D with the different voids in it. In 2, the Pb(II) center is eight coordinate, with the coordination sites being occupied by O anchors of the oda ligand and N terminals of the phen ligand. The phen ligands in abutting assemblies of the crystal lattice in 2 are parallel to each other and participate in weak π-π stacking interactions, which further contribute to the stability of the compound.

It is worth mentioning that the oda ligand is doubly

deprotonated as in 1, but the coordination mode is different from that in 1. Furthermore, an interesting feature in 2 is the fact that only the carboxylato oxygen atoms participate in the coordination sphere of Pb(II) ions, in stark contrast to the corresponding binding mode of the same ligand in 1.


Page 17 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


17 In the chemical reactivity of the binary system Pb(II)-tda leading to the binary species [Pb(tda)]n (3), the Pb(II) center is seven coordinate, with the coordination sites being occupied by O and S anchors of the tda ligand. The coordination mode of the tda ligand here is unique as shown in Scheme 1, with both carboxylato oxygen and sulfur ether atoms participating in the coordination sphere of Pb(II). In the ternary Pb(II)-tda-phen system leading to the metal-organic hybrid polymer [Pb(phen)(tda)]n (4), the Pb(II) center is six coordinate, with the coordination sites occupied by O anchors of the tda ligand and N terminals of the phen ligand. The coordination mode of the tda ligand here is also uniquely defined as shown in Scheme 1, but different from the one in 3. The tda ligand in 4 is coordinated to Pb(II) ions only through the carboxylato oxygen atoms leaving the ether sulfur atoms out of the coordination sphere of Pb(II) ions. Collectively, in the binary Pb(II)-(O,S)dicarboxylic acid systems a) the oda and tda ligands are coordinated to the Pb(II) ions through both carboxylato and ether heteroatoms (-O, -S) (1 and 3), and b) the arising molecular assemblies differ in the repeating unit nuclearity (with difference linked to the presence of the different nature of the heteroatoms in the dicarboxylic acid ligands and the associated chemical reactivity).

In the case of the ternary Pb(II)-phen-(O,S)dicarboxylic acid systems, a)

mononuclear assemblies of Pb(II) emerge in both (O-,S-)-containing dicarboxylic acids (2 and 4), and b) both O- and S-containing ligands bind Pb(II), with the heteroatoms (O in 2 and S in 4) in the O- and Scontaining dicarboxylate ligands abstaining from the coordination sphere of Pb(II), leading to metalorganic hybrid polymers with distinct lattice architectures different from those in 1 and 3. The coordination geometry of Pb(II).

The coordination geometry of the PbOn polyhedra in Pb(II)

materials can be described as hemidirected for low coordination numbers (2–5), holodirected for high coordination numbers (9,10), with either a hemidirected or holodirected stereochemistry being observed for intermediate coordination numbers (6–8).

44,45

It has been found through ab initio molecular orbital

calculations on Pb(II) complexes in the gas-phase that a hemidirected geometry occurs if the ligands are hard, the ligand coordination number is low and attractive interactions exist between the ligands.

46,47

To

this end, in 1, the seven-coordinate Pb(1) and Pb(2) centers exhibit a hemidirected geometry, with the nine-coordinate Pb(3) centers displaying a holodirected geometry. The eight coordinate Pb(II) centers in 2 exhibit a hemidirected geometry. For the seven coordinate Pb(II) centers in 3, a hemidirected geometry is observed. Finally, the six-coordinate Pb(II) centers in 4, exhibit a hemidirected geometry. In view of the aforementioned assignments on the coordination geometry of the title complexes, the X-ray crystal structures of the investigated species concur with the analytical and physicochemical data (FT-IR and solid-state NMR) on all four species. To this end, outstanding information emerges from the NMR of the coordination compounds in the solid state, with the

13

C and

207

Pb signals in the NMR spectra denoting the

coordination geometry observed in the investigated centers of the corresponding lattice architectures. On the basis of past reports, various patterns had been observed, earmarking specific regions in the spectrum for five up to ten coordinate Pb(II) ions.

48,49,50,51

207

Pb

Consistent with the above information, ten .

coordinate Pb(II) compounds exhibit resonances as follows: [Pb2(HArg)3(H2O)(NO3)7] 3H2O Pb1: -1285 ppm and Pb2: -2511 ppm.

49

Eight coordinate Pb(II) compounds show resonances as follows:



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 48

18 [Pb(OH2)2(Val)(Ile)(NO3)2] (from -1950 to -1790 ppm). as

follows:

[Pb(leu)(NO3)]

[Pb(Hasp)(NO3)]

(-2439

ppm),

resonances

.

49

(-929

49

Seven coordinate Pb(II) compounds exhibit

ppm)

[Pb(Hile)2(NO3)(H2O)2]NO3

[Pb2(Hval)5](ClO4)4·2H2O

(from

49

-1390

[Pb(OH2)(Ile)2][NO3]2 H2O (-1766 ppm), while six coordinate Pb(II) species exhibit

to 207

the present work, the arisen

Pb 49

(-1774

ppm),

-1755)

ppm),

49

Pb resonances at a

lower field, with a representative species being [Pb(OH2)2(Val)2(NO3)]NO3 (-1707 ppm) (vide infra). 207

207

49

In

Pb data represent coordination numbers, six (4), seven [Pb1(1), Pb2(1),

(3)], eight (2) and nine (Pb3(1)), thereby earmarking the importance of that nucleus in the detection of specific lattice structural properties of Pb(II)-containing inorganic–organic hybrid materials. It should be emphasized, however, that there are no clear boundaries for shift ranges of specific coordination numbers; the fact that the shift range of a specific coordination number is so large for Pb(II) may also mean that coordinating atoms have a strong effect and the latter could override a clear assignment of the coordination number (vide supra coordination number 7 at -929 and -2439 ppm). More work in this direction is under way in our labs. Lattice architecture and dimensionality in (O,S)-dicarboxylic acid binary and ternary systems of Pb(II) involving phen The chemical reactivity in the binary Pb(II)-(O)-oda acid system leads to a molecular type of lattice architecture exemplified through [Pb3(oda)3]n (1).

The salient features of such an assembly with a

trinuclear Pb(II) repeating unit include a) a doubly deprotonated oda acid coordinated to the metal of Pb(II) through the carboxylato oxygen atoms, and b) involvement of the ether O-heteroatom in the coordination sphere of Pb(II) centers, ultimately giving rise to a 3D crystal lattice. In the case of the corresponding Scontaining tda acid system, the S heteroatom presents a similar binding behavior with its O-linked congener. In fact a) the S heteroatom of the Pb(II)-bound ligand did participate in the coordination sphere of Pb(II), and b) the repeating unit of the metal organic framework hybrid material was a mononuclear entity, ultimately giving rise to a 2D crystal lattice architecture (3). Turning to ternary systems, the chemical reactivity of Pb(II) toward oda with phen led to a ternary species, still polymeric, with the aromatic chelator inducing changes not so much on the polymeric nature of the final material but mostly on a) the nuclearity of the arising preparing unit (mononuclear), and b) the ether oxygen atom of oda abstaining from coordination to the Pb(II), likely because of the size and bulk of the phen ligand. Hence, the final structure of the material (2) displays a 2D lattice architecture, which further extends into the third dimension (a 3D lattice) through the action of the π-π interactions of the bound phen ligand. In the case of the S-congener tda acid participating in the ternary Pb(II)-tda-phen system, the emerging material 4 exhibits a) a mononuclear Pb(II) assembly, b) a S-heteroatom abstaining from coordination to the Pb(II), and c) a 1D lattice dimensionality being raised to 2D through the involvement of π-π interactions of the bound phen ligand. Structural differences between O-/S-containing lattice structures and luminescence properties There is a clear reduction in dimensionality of the lattice architecture of the materials arising through the (O,S)-dicarboxylic acid reactivity with Pb(II) when “binary” turns “ternary” upon phen incorporation into the metal ion coordination sphere. Specifically, a 3D lattice in 1 turns into a 2D lattice in 3 through a mere


Page 19 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


19 change in the nature of the heteroatom (from O in 1 to S in 3) in the oda acid ligand. In the case of the ternary systems involving oda and tda, lattice dimensionality is reduced upon O vs. S replacement as the heteroatom in the oda acid ligand. Thus, from an overall 3D lattice dimensionality in 2 one ends up with an overall 2D lattice dimensionality in 4. Thus, reduction in dimensionality persists both in the absence and presence of the π-π interactions involved in the interactions shaping the architecture of the lattices emerging from oda and tda ligands reacting with Pb(II) in the presence of phen. Quite interestingly, it appears that introduction of phen into the reactivity of the binary systems of Pb(II) with either oda or tda does not lead to a reduction in lattice dimensionality of the corresponding ternary lattice, when π-π interactions are taken into consideration.

Undoubtedly, the difference in a) size between O- and S-

heteroatoms in the congener oda and tda ligands, and b) bond distances between Pb(II) and the ether heteroatom, Pb(II)-O (2.619(5)-2.811(7) (Å)) for 1 and Pb(II)-S (3.087(3) (Å)) for 3, respectively, c) the absence and presence of the aromatic phen chelator (and by extension the establishment of π-π interactions), and d) the interplay between O vs. S and phen steric congestion in the coordination sphere of Pb(II) centers, collectively formulate 1. the coordination environment and number of Pb(II) centers in the materials at hand, and 2. the variability of coordination environment linked to the nuclearity of the assembly in the repeating unit(s) of the coordination polymers isolated from the chemical reaction mixtures investigated. The photoluminescence properties of 1-4 appear to vary in line with the nature of the ligand used. Free oda ligand does not possess any luminescence at room temperature, when in fact both 1 and 2 exhibit very strong bands between 200-800 nm.

In [Pb3(oda)3]n (1), two emission bands emerge, while in

[Pb(phen)(oda)]n (2) there is only one strong emission band, with spectral features in both cases potentially reflecting ligand-to-metal-charge-transfer (LMCT) processes. In addition, bearing in mind the fact that phen itself exhibits a strong emission band at 417 nm (λex 368 nm), it can be argued that the band at 574 nm for 2 is red–shifted and may also be linked to an interligand fluorescence emission.

52,53,54

In the

case of 3 and 4, there are emission features in the visible region reminiscent of the free ligand, but it cannot be unequivocally stated whether they reflect enhancement or quenching process due to the fact that the relative intensity is almost the same in both the ligand and the metal-organic hybrid polymer. Collectively, therefore, a) oda and phen binding into the coordination sphere of Pb(II) brings about luminescence activity, discrete in each case, b) tda binding does not clearly induce ostensible luminescence activity changes in the S-congener metal-organic hybrid polymers, thereby reflecting the unique character of lattice architecture in the O- and S-containing heteroatom ligands bound to Pb(II) and the coordination modes through which the respective lattice assembly arises. Conclusions pH-Specific hydrothermal synthetic reactivity investigation of oda and tda acids with Pb(II) and phen afforded four distinctly composed metal-organic hybrid polymers 1-4.

The arisen binary and ternary

polymers present unique assemblies of inorganic-organic complex repeating units reflecting the a) the structural features of the oda and tda ligands employed, and b) the nature of the ether heteroatom (O vs. S) ultimately affecting the nature of the emerging crystalline lattices in 1-4. It appears that under defined



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 48

20 pH and molecular stoichiometry reactivity conditions, the arising species possess unique lattice architectures consistent with the composition and nuclearity of their repeating unit complex assemblies. In turn, lattice dimensionality follows suit with a) defined changes at the binary and ternary level, b) reduction in dimensionality (both at the binary and ternary level) upon switching from O-oda to S-containing tda ligands, and b) π-π interactions playing important roles in bestowing lattice identity and dimensionality at the ternary level upon phen incorporation in the respective lattices. Linked to these structural features are a) spectroscopic FT-IR,

13

C- and

207

Pb-NMR signatures verifying the unique identity and providing distinct

spectroscopic fingerprints of the respective lattices examined, and b) luminescent properties ear-tagging the structural lattice architecture of the O- and S-containing Pb(II)-organic hybrid materials. The well-defined structural and spectroscopic signatures of the title materials denote the interplay of the aforementioned factors arising from the O- vs. S- substitution in the dicarboxylic oda and tda ligands seeking binding toward Pb(II) and bestowing variable yet distinct dimensionality (2D-3D) in the lattice architectures arisen. In line with these findings, the nature of the heteroatom in connection with the chemical and structural features (length of C-chain, branching, hydrophilicity, etc.) of the ligands themselves stand to influence the emerging lattice assembly in binary and ternary systems of Pb(II), thereby affecting the nature and physicochemical properties of the ultimate products. The systematic investigation into such parameters bearing on the nature of new functional hybrid materials of Pb(II), correlating lattice identity and dimensionality with spectroscopic activity (e.g. photoactivity), are currently under investigation in our lab.

Acknowledgements This work was co-financed by the EU–ESF and Greek national funds through the NSRF-Heracleitus II program. The award of a research fellowship of excellence by the Research Committee of Aristotle U. of Thessaloniki to C. Gabriel is gratefully acknowledged. The DFG (German Research Foundation) and the Experimental Physics Institutes of Leipzig University are acknowledged for their support with the Avance 750 MHz NMR spectrometer. Supporting Information Description: X-ray crystal crystallographic files, in CIF format, (CCDC 917912 (1), 917913 (2), 917914 (3), and 917915 (4)), and listings of positional and thermal parameters and Hbond distances and angles for 1-4.

The material is available free of charge via Internet at

http://pubs.acs.org. References [1]

Fan, S.-R.; Zhu, L.-G. Inorg. Chem. 2007, 46, 6785-6793.

[2]

Pellissier, A.; Bretonniere, Y.; Chatterton, N.; Pecaut, J.; Delangle, P.; Mazzanti, M. Inorg. Chem. 2007, 46, 3714-3725.

[3]

Andersen, R. J.; Targiani, R. C.; Hancock, R. D.; Stern, C. L.; Goldberg, D. P.; Godwin, H. A. Inorg. Chem. 2006, 45, 6574-6776.


Page 21 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


21

[4]

Buston, J. E. H.; Claridge, T. D. W.; Heyes, S. J. ; Leech, M. A.; Moloney, M. G.; Prout, K.; Stevenson, M. Dalton Trans. 2005, 3195-3203.

[5]

Gabriel, C.; Raptopoulou, C. P.; Psycharis, V.; Terzis, A.; Zervou, M.; Salifoglou A. Crystal Gro. Design 2011, 11(2), 382-395.

[6]

Cambridge Structural Database System, Cambridge Crystallographic data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (updated 2011).

[7]

Metz, G.; Wu, X. L.; Smith S. O. J. Magn. Reson. A, 1994, 110, 219-227.

[8]

Neue, G.; Dybowski, C.; Smith, M. L.; Hepp, M. A.; Perry, D. L. Solid State Nucl. Magn. Reson. 1996, 6, 241-250.

[9]

Massiot, D.; Fayon, F.; Capron, M.; King, I.; Le Calvé, S.; Alonso, B.; Durand, J-O.; Bujoli, B.; Gan, Z.; Hoatson, G. Magn. Res. Chem. 2002, 40, 70-76.

[10]

Haeberlen, U. In: Advances in Magnetic Resonance, Suppl. 1, J. S. Waugh, Ed; Academic Press: New York, 1976.

[11]

Rigaku/MSC (2005). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.

[12]

Sheldrick, G. M. SHELXS-97: Structure Solving Program; University of Göttingen, Germany, 1997.

[13]

Sheldrick, G. M. SHELXL-97: Structure Refinement Program; University of Göttingen, Germany, 1997.

[14]

DIAMOND – Crystal and Molecular Structure Visualization, Ver. 3.1, Crystal Impact, Rathausgasse 30, 53111, Bonn, Germany.

[15]

Chen, Y.-L.; Wang, L.; Yu, L.-X.; Fan, Y.; Shi, J.; Yang, H.; Jiang, J.-H.; Wang, W.; Zhang, P.; Zhang, L.- R. J. Coord. Chem. 2010, 63, 2079–2087.

[16]

Svensson, G.; Olson S.; Albertsson, J. Acta Chem. Scand. 1998, 52, 868-872.

[17]

Norberg, S.; Svensson G.; Albertsson, J. Acta Cryst. 1999, C55, 356-358.

[18]

Gabriel, C.; Perikli, M.; Raptopoulou, C. P.; Terzis, A.; Psycharis, V.; Mateescu, C.; Jakusch, T.; Kiss, T.; Bertmer, M.; Salifoglou, A. Inorg. Chem. 2012, 51, 9282−9296.

[19]

Zhao, Y. H.; Su, Z. M.; Wang, Y.; Fu, Y. M.; Liu, S. D.; Li, P. Inorg. Chem. Comm. 2007, 10, 410414.

[20]

Zhang, K.-L.; Liang, W.; Chang, Y.; Yuan, Li.-M.; Ng, W.S. Polyhedron 2009, 28, 647–652.

[21]

Foreman, M. St. J.; Plater, M. J.; Skakle, M. S. J. Chem. Soc., Dalton Trans. 2001, 1897-1903.

[22]

Soudi, A. A.; Marandi, F.; Ramazani, A.; Ahmadi, E.; Morsali, A. C. R. Chimie 2005, 8, 157-168.

[23]

Kourgiantakis, M.; Matzapetakis, M.; Raptopoulou, C. P.; Terzis, A.; Salifoglou, A. Inorg. Chim. Acta 2000, 297, 134-138.

[24]

Jiang, C,; Zhu, X.; Yu, Z.-P.; Wang, Z.-Y. Inorg. Chem. Comm. 2003, 6, 706–709.

[25]

a) Jiang, C.; Wang, Z.-Y. Polyhedron 2003, 22, 2953-2959.; b) Wu, Z.-Y.; Xue, Y.-H.; Xu, D.-J. Acta Cryst. 2003, E59, m809-m811.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 48

22

[26]

a) Whitlow, S.; Davey, G. J. Chem. Soc. Dalton Trans. 1975, 1228-1232.; b) Baggio, R.; Calvo, R.; Garland, M.T.; Peña, O.; Perec, M.; Slep, L. D. Inorg. Chem. Comm. 2007, 10, 1249–1252.

[27] Grirrane, A.; Pastor, A.; Mealli, C.; Ienco, A. Rosa, P.; Prado-Gotor, R.; Galindo A. Inorg. Chim. Acta 2004, 357, 4215–4219. [28]

Grirrane, A.; Pastor, A.; ÁIvarez, E.; Mealli, C.; Ienco, A. Rosa, P.; Montilla, F.; Galindo A. Eur. J. Inorg. Chem. 2004, 707-717.

[29]

a) Baggio, R.; Garland, M. T.; Perec M. Inorg. Chim. Acta 2000, 310, 103–109.; b) Baggio, R.; Garland, M. T.; Perec M. Acta Cryst. 2003, C59, m30-m32.; c) Baggio, R.; Garland, M. T.; Perec M.; Vega, A. Inorg. Chem. 1995, 34, 1961-1963.

[30] Grirrane, A.; Pastor, A.; Álvarez, E.; Mealli, C.; Ienco, A.; Masi, D.; Galindo, A. Inorg. Chem. Comm. 2005, 8, 463–466. [31]

a)

Alarcón-Payer, C.; Pivetta, T.; Choquesillo-Lazarte, D.; González-Pérez, J.M.; Crisponi, G.;

Castiñeiras, A.; Niclós-Gutiérrez, J. Inorg. Chim. Acta 2005, 35, 1918–1926.; b) Baggio, R.; Garland, M. T.; Manzur, J.; Peña, O.; Perec, M.; Spodine, E.; Vega, A. Inorg. Chim. Acta 1999, 286, 74–79. [32]

larcón-Payer, C.; Pivetta, T.; Choquesillo-Lazarte, D.; González-Pérez, J.M.; Crisponi, G.; Castiñeiras, A.; Niclós-Gutiérrez, J. Inorg. Chem. Comm. 2004, 7, 1277–1280.

[33]

Wu, M.C.; Lee, C.S. Inorg. Chem. 2006, 45, 9634-9636.

[34]

Fallon, G. D.; Spiccia, L.; West, B. O.; Zhang, Q. Polyhedron 1997, 16, 19-23.

[35]

Greer, B. J.; Michaelis, V. K.; Katz, M. J.; Leznoff, D. B.; Schreckenbach, G.; Kroeker, S. Chem. Eur. J. 2011, 17, 3609–3618.

[36]

Thangadurai, P.; Ramasamy, S.; Manoharan, P.T. Eur. Phys. J. B 2004, 37, 425–432

[37]

Kye, Y.-S.; Connolly, S.; Herreros, B.; Harbison, G.S. Main Group Metal Compounds 1999, 22, 373-378.

[38]

Niessen, H.G.; Van Buskirk, M.; Dybowski, C.; Corbin, D.R.; Reimer, J.A.; Bell, A.T. J. Phys. Chem. B 2001, 105, 2945-2950.

[39] Zhang, W.H.; Wang, Y.Y.; Lermontova, E. Kh.; Yang, G. P.; Liu, B.; Jin, J. C.; Dong, Z.; Shi, Q. Z. Cryst. Growth Des. 2010, 10, 76–84. [40]

Jin, J. C.; Wang, Y. Y.; Zhang, W. H.; Lermontov, A. S.; Lermontova, E. Kh.; Shi, Q. Z. Dalton Trans., 2009, 10181-10191.

[41]

Zhang, W. H.; Dong, Z.; Wang, Y. Y.; Hou, L.; Jin, J. C.; Huang, W. H.; Shi, Q. Z. Dalton Trans., 2011, 40, 2509-2521.

[42]

Dai, J.C.; Wu, X.T.; Fu, Z.Y.; Hu, S.M.; Du, W.X.; Cui, C.P.; Wu, L.M.; Zhang, H.H.; Sun, R.Q. Chem. Commun. 2002, 12-13.

[43]

Tao, J.; Tong, M.L.; Shi, J.X.; Chen, X.M.; Ng, S.W. Chem. Commun. 2000, 2043-2044.


Page 23 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


23

[44]

Ayyappan, S.; Diaz de Delgado, G.; Cheetham, A.K.; Fιrey, G.; Rao, C.N.R. J. Chem. Soc., Dalton Trans. 1999, 2905-2907.

[45]

Glowiak, T.; Kozlowski, H.; Erre, L.S.; Micera, G.; Gulinati, B. Inorg. Chim. Acta 1992, 202, 43-48.

[46]

Livny, L.S.; Glusker, J.P.; Bock, C.W. Inorg. Chem. 1998, 37, 1853-1867.

[47]

Watson, C.W.; Parker, S.C. J. Phys. Chem. B. 1999, 103, 1258-1262.

[48]

Gasque, L. ; Verhoeven, M. A.; Bernès, S.; Barrios, F.; Haasnoot, J. G.; Reedijk, J. Eur. J. Inorg. Chem. 2008, 4395–4403.

[49]

Saunders, C. D. L. Ph.D. Thesis, 2009.

[50]

Beckmann, P. A.; Dybowski, C. J. Mag. Reson. 2000, 146, 379-380.

[51]

Nowotny, H.; Heger, G. Acta. Cryst. 1986, C42, 133-135.

[52]

Chen, W.; Wang, J. Y.; Chen, C.; Yue, Q.; Yuan, H. M.; Chen, J. S.; Wang, S. N. Inorg. Chem. 2003, 42, 944-946.

[53]

Chen, Z. F.; Xiong, R. G.; Zhang, J.; Chen, X. T.; Xue, Z. L.; You, X. Z. Inorg. Chem. 2001, 40, 4075-4077.

[54]

Dai, J. C.; Wu, X. T.; Fu, Z. Y.; Cui, C. P.; Hu, S. M.; Du, W. X.; Wu, L. M.; Zhang, H. H.; Sun, R. Q. Inorg. Chem. 2002, 41, 1391-1396.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 48

24 Table 1: Summary of Crystal, Intensity Collection and Refinement Data for [Pb3(oda)3]n (1), [Pb(phen)(oda)]n (2), [Pb(tda)]n (3), and [Pb(phen)(tda)]n (4). 1

2

3

4

C12H12O15Pb3

C16H12O5Ν2Pb

C4H4O4SPb

C16H12O4Ν2SPb

formula mass

1017.79

519.47

355.32

535.55

T, K

293 (2)

180 (2)

180 (2)

180 (2)

MoKα 0.71073

MoKα 0.71073

MoKα 0.71073

MoKα 0.71073

Pī

C2/c

Iba2

Pī

a (Ǻ)

7.6283(2)

10.253(2)

19.2954(16)

8.3461 (2)

b (Ǻ)

10.8525(2)

20.192(4)

9.0591(5)

8.7744(2)

c (Ǻ)

12.9010(3)

8.337(2)

7.5483(4)

10.9103(2)

α, deg

114.352(1)

90.00

90.00

76.023(1)

β, deg

94.039(1)

117.41(1)

90.00

80.584(1)

γ, deg

91.236(1)

90.00

90.00

77.734(1)

3

969.08(4)

1532.2(6)

1319.37(15)

752.30(3)

2

4

8

2

3.488

2.252

3.578

2.364

26.073

11.041

25.837

11.377

formula

wavelength, λ (Ǻ) space group

V, (Ǻ ) Z -3

Dcalcd (Mg m ) abs.coeff. (µ), mm R indices

-1

R = 0.0276

(1)

Rw = 0.0675

R = 0.0285

(2)

Rw = 0.0722

o

2θmax

R = 0.0296

(2)

Rw = 0.0667

o

R = 0.0149

(2)

Rw = 0.0339

o

(2)

o

55

52

52

52

number of reflections

31021/4415[R(int)

8555/1498[R(int)

3006/1251[R(int) =

15398/2955[R(int)

collected/unique/used

= 0.0563]/4415

= 0.0523]/1498

0.0436]/1251

= 0.0389]/2955

3

(∆ρ)max/(∆ρ)min

(1)

1.6107/-1.054 e/Å

0.721/-0.631 e/Å

1.135

1.160

1.042

1.086

0.0294/0.0683

0.0286/0.0723

0.0311/0.0675

0.0163/0.0344

R values are based on F values, Rw values are based on F .

∑F −F ∑(F ) o

c

o

,

3

1.742/-1.166 e/Å

2

R= (2)

3

1.807/-1.257e/Å

GOF R/Rw (for all data)

3

Rw =

∑ [w( F

2 o

− Fc2 ) 2

]

∑ [w( F ) ] 2 2 o

[(1):4176, (2):1494, (3):1195, and (4):2835 refs I>2σ(I)]


Page 25 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


25 Table 2: Bond lengths [Å] and angles [deg] for [Pb3(oda)3]n (1) Distances (Å) Pb(1)-Ο(1)

2.494(5)

Pb(2)-Ο(23'')

2.652(5)

Pb(1)-Ο(11)

2.538(6)

Pb(2)-Ο(22'''')

2.659(5)

Pb(1)-O(21)

2.592(6)

Pb(3)-Ο(15*)

2.551(6)

Pb(1)-O(4)

2.619(5)

Pb(3)-Ο(5**)

2.554(5)

Pb(1)-Ο(3)

2.619(5)

Pb(3)-Ο(25***)

2.585(5)

Pb(1)-O(1’)

2.695(5)

Pb(3)-Ο(11*)

2.596(7)

Pb(1)-Ο(12)

2.818(1)

Pb(3)-Ο(5)

2.633(6)

Pb(2)-Ο(22'')

2.458(5)

Pb(3)-Ο(13*)

2.811(7)

Pb(2)-Ο(2)

2.551(6)

Pb(3)-Ο(24****)

2.817(7)

Pb(2)-Ο(15''')

2.633(6)

Pb(3)-Ο(25****)

2.762(8)

Pb(2)-Ο(14''')

2.645(7)

Pb(3)-Ο(4)

2.862(5)

Pb(2)-Ο(24'')

2.646(6) o

Angles ( ) Ο(1)-Pb(1)-O(11)

123.6(2)

O(14''')- Pb(2)-O(24'')

93.1(2)

Ο(1)-Pb(1)-O(21)

86.4(2)

O(22'')- Pb(2)-O(23'')

60.9(2)

O(11)- Pb(1)-O(21)

147.8(2)

O(2)- Pb(2)-O(23'')

86.1(2)

Ο(1)-Pb(1)-O(4)

120.5(2)

O(15''')- Pb(2)-O(23'')

104.0(2)

O(11)- Pb(1)-O(4)

78.6(2)

O(14''')- Pb(2)-O(23'')

70.4(2)

O(21)- Pb(1)-O(4)

75.3(2)

O(24'')- Pb(2)-O(23'')

59.7(2)

Ο(1)-Pb(1)-O(3)

60.9(2)

O(22'')- Pb(2)-O(22'''')

65.4(2)

O(11)- Pb(1)-O(3)

101.6(2)

O(2)- Pb(2)-O(22'''')

109.9(2)

O(21)- Pb(1)-O(3)

81.9(2)

O(15''')- Pb(2)-O(22'''')

92.9(2)

O(1)- Pb(1)-O(3)

60.9(2)

O(14''')- Pb(2)-O(22'''')

81.9(2)

O(1)- Pb(1)-O(1’)

65.5(2)

O(24'')- Pb(2)-O(22'''')

173.1(2)

O(11)- Pb(1)-O(1’)

89.2(2)

O(23'')- Pb(2)-O(22'''')

122.3(3)

O(21)- Pb(1)-O(1’)

116.5(2)

O(15*)-Pb(3)-O(5**)

83.4(2)

O(4)- Pb(1)-O(1’)

167.8(2)

O(15*)- Pb(3)-O(25***)

87.7(2)

O(3)- Pb(1)-O(1’)

121.6(2)

O(5**)- Pb(3)-O(25***)

165.4(2)

O(22'')-Pb(2)-O(2)

85.8(2)

O(15*)- Pb(3)-O(11*)

115.2(2)

O(22'')- Pb(2)-O(15''')

128.5(2)

O(5**)- Pb(3)-O(11*)

87.1(2)

O(2)- Pb(2)-O(15''')

145.1(2)

O(25***)- Pb(3)-O(11*)

86.1(2)

O(2)- Pb(2)-O(14''')

156.4(2)

O(15*)- Pb(3)-O(5)

83.7(2)

O(15''')- Pb(2)-O(14''')

49.1(2)

O(5)- Pb(3)-O(5*)

70.9(2)

O(22'')- Pb(2)-O(24'')

118.6(2)

O(25***)- Pb(3)-O(5)

119.7(2)



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 48

26 O(2)- Pb(2)-O(24'')

76.4(2)

O(15''')- Pb(2)-O(24'')

80.2(2)

Symmetry operations:

O(11*)- Pb(3)-O(5)

149.7(2)

(') -x, 1-y, 1-z; ('') x, 1+y, z; (''') 1+x, 1+y, 1+z; ('''') 1-x, 1-y, 1-z; (*) -x, -y, -z; (**) 1-

x, -y, -z; (***) -x, -y, 1-z; (****) x, y, -1+z;


Page 27 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


27 Table 3: Bond lengths [Å] and angles [deg] for [Pb(phen)(oda)]n (2). Distances (Å) Pb-N(1)

2.544(5)

Pb-O(11)

2.635(4)

Pb-O(12')

2.638(6)

Pb-O(12)

2.747(6)

o

Angles ( ) N(1)-Pb-N(1')

64.7(2)

O(11)-Pb-O(11'')

150.0(2)

N(1)-Pb-O(12''')

145.5(2)

N(1)-Pb-O(12)

82.6(2)

N(1)-Pb-O(12')

83.4(2)

N(1)-Pb-O(12'')

117.9(2)

N(1'') -Pb-O(12''')

83.4(2)

O(12)-Pb-O(12''')

102.7(2)

N(1'')-Pb-O(12')

145.5(2)

O(12)-Pb-O(12')

67.2(2)

O(12')-Pb-O(12''')

130.3(2)

O(11)-Pb-O(12'')

141.8(2)

N(1)-Pb- O(11'')

75.0(2)

O(11)-Pb-O(12)

46.9(2)

N(1)-Pb- O(11)

79.7(2)

N(1'')-Pb-O(12)

117.9(2)

O(12')-Pb- O(11)

113.3(2)

N(1'')-Pb-O(12'')

82.6(2)

O(12')-Pb-O(11'')

79.7(2)

O(12'')-Pb-O(12''')

67.2(2)

N(1'')-Pb-O(11'')

79.7(2)

O(12')-Pb-O(12'')

102.7(2)

N(1'')-Pb-O(11)

75.0(2)

O(11'')-Pb-O(12'')

46.9(2)

O(12''')-Pb-O(11)

79.7(2)

O(11'')-Pb-O(12)

141.8(2)

O(12''')-Pb-O(11'')

113.3(2)

O(12)-Pb-O(12'')

157.0(3)

Symmetry operations: (') -x, -y, 1-z; ('') -x, y, 1.5-z; (''') x, -y, 0.5+z.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 48

28 Table 4: Bond lengths [Å] and angles [deg] for [Pb(tda)]n (3). Distances (Å) Pb-Ο(4)

2.404(8)

Pb-Ο(3''')

2.522(7)

Pb-Ο(2)

2.606(8)

Pb-O(1')

2.841(7)

Pb-O(2'')

2.681(7)

Pb-S

3.087(3)

Pb-O(1'')

2.664(8) o

Angles ( ) Ο(4)-Pb-O(3''')

77.3(3)

O(2)-Pb-O(2'')

126.8(2)

Ο(4)-Pb-O(2)

83.1(2)

O(1)-Pb-O(2)

49.1(2)

O(3''')- Pb-O(2)

131.1(2)

O(4)-Pb-S

65.4(2)

Ο(4)-Pb-O(1'')

72.4(2)

O(3''')-Pb-S

66.9(2)

O(3''')-Pb-O(1'')

133.9(2)

O(2)-Pb-S

64.2(2)

O(2)-Pb-O(1')

78.3(2)

O(1'')-Pb-S

125.8(2)

Ο(4)-Pb-O(2'')

72.7(2)

O(2'')-Pb-S

135.0(2)

O(3''')-Pb-O(2'')

89.1(2)

Symmetry operations: (') x, -2-y, -0.5+z; ('') -1.5-x, 0.5+y, z; (''') x, -1-y, -0.5+z.

Table 5: Bond lengths [Å] and angles [deg] for [Pb2(phen)2(tda)2]n (4). Distances (Å) Pb-N(1)

2.608(2)

Pb-O(23'')

2.491(2)

Pb-N(2)

2.656(2)

Pb-O(24')

2.750(2)

Pb-O(22)

2.313(2)

Pb-O(21)

2.785(3)

o

Angles ( ) O(22)-Pb-O(23'')

90.77(8)

N(1)-Pb-N(2)

63.03(7)

O(22)-Pb-N(1)

77.18(7)

O(22)-Pb-O(24')

83.61(7)

O(23'')-Pb-N(1)

78.19(7)

O(23'')-Pb-O(24')

140.92(7)

O(22)-Pb-N(2)

87.14(7)

N(1)-Pb-O(24')

136.81(7)

O(23'')-Pb-N(2)

140.64(7)

N(2)-Pb-O(24')

77.86(7)

Symmetry operations: (') 1-x, 1-y, -z; ('') x, 1+y, z.


Page 29 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


29 Table 6. M-O terminal and ether bond distances (Å) in M-oda complexes. Compounds

M-O

M-O(ether)

[Pb3(oda)3]n (1)

2.458(5)-2.862(5)

2.619(5)-2.811(7)

[Pb(phen)(oda)]n (2)

2.635(4)-2.747(6)

----------

15

2.425(7)-2.743(8)

2.648(8)

2.464(13)-2.890(13)

2.77(2)

[Pb(oda)]

.

Pb4(oda)3(NO3) H2O [Pb(oda)(H2O)

16

17

24 [Cd(µ-H2O)(oda)2(H2O)2]n

.

25 {[Co(oda)(H2O)2] H2O}n

.

[Co(oda)(phen)H2O] 1.5H2O [Cu(oda)] 1/2H2O

25

26

2.490(3)-2.91(2)

2.554(10)

2.218(4)-2.377(4)

2.399(4)

2.0345(14)-2.1213(15)

2.073(3)

2.070(2)-2.130(2)

2.118(2)

1.941(9)-2.73(2)

2.488(4)

26

1.937(3)-2.333(5)

2.486(4)

27 [{Fe(oda)(H2O)2} H2O]n

2.027(2)-2.168(2)

2.130(2)

2.114(3)-2.230(3)

2.304(4)

2.1798(17)-2.1876(17)

2.230(3)

2.006(3)-2.038(3)

2.130(3)

2.062(4)-2.091(4)

2.061(4)

.

[Cu(oda)(phen)] 3H2O .

24 [Mn(µ-H2O)(oda)2(H2O)2]n

[{Mn(oda)(phen)}·4H2O]n [Ni(oda)(H2O)3]·1.5H2O

28

29

[Ni(oda)(phen)(H2O)]·1.5H2O .

29 {[Zn(oda)(H2O)2] H2O}n

.

[Zr{oda}2(H2O)2] 4H2O

29

29

2.0143(14)-2.1272(17) 2.134(3)-2.166(2)


2.1143(15) 2.282(2)


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 48

30 Table 7. M-O terminal and M-S ether bond distances (Å) in M-tda complexes.

Compounds

M-O

M-S (ether)

[Pb(tda)]n (3)

2.404(8)-2.841(7)

3.087(3)

[Pb(phen)(tda)]n (4)

2.313(2)-2.785(3)

-----------

30 [Co(tda)(H2O)]n

2.029(2)-2.091(2)

2.508(1)

1.951(3)-1.965(3)

2.570(1)

1.974(2)-2.320(3)

2.7242(13)

2.034(1)-2.066(1)

2.415(1)

2.049(5)-2.121(5)

2.5232(19)

31 [Cu(tda)]n 31

[Cu(tda)(phen)]2·H2tda .

[Ni(tda)(H2O)3] H2O Zn(tda)H2O

33

32


Page 31 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


31 FIGURE CAPTIONS Figure 1:

Labeled plot of different parts of the structure of 1. The insets of Figures (1A), (1B) and (1C) display the polyhedra around Pb(1), Pb(2), and Pb(3) atoms, respectively. (1A) Partially labeled plot showing the coordination environment around Pb(1), the tridentate chelator 2

2

2

around each Pb(II) atom of oda (-2) ligands as well as the µ5-κ O:κ O':κ O'':κO''':κO'''' and µ32

2

κ O:κ O':κO'':κO''':κO'''' coordination modes. (1B) Partially labeled plot showing the coordination environment around Pb(2). (1C) Partially labeled plot showing the coordination environment around Pb(3). Symmetry operations: ('): -x, 1-y, 1-z; (''): x, 1+y, z; ('''): 1+x, 1+y, 1+z; (''''): 1-x, 1-y, 1-z ; (*): -x, -y, -z; (**):1-x, -y, -z; (***): -x, -y, 1-z; (****): x, y, -1+z; (!):1+x,1+y,1+z; (!!): -x,1-y,1-z; ( !!!): -x,y,1+z ;(&):-1+x,-1+y,-1+z. Hydrogen atoms have been omitted for clarity. (1D) Arrangement of polyhedra around Pb(1) (magenta), Pb(2) (green) and Pb(3) (blue) atoms in the unit cell of 1. (1E) 3D lattice architecture of the structure in 1. Figure 2:

Types of metallacyclic rings (A-D) in the structure of 1.

Figure 3: (A) Partially labeled plot of a very small fragment of the structure in 2. Hydrogen atoms have been omitted for clarity. Symmetry operations: ('): -x, -y, 1-z; (''): –x, y, 1.5-z; ('''): x, -y, 0.5+z; (''''): 1-x, y, 1.5-z; (*): 1+y, y, z; (**): 1-x,-y, 1-z; (***): -1-x,-y, 1-z; (****): -1+x, y,z. (B) Plot of the 2D network of 2 extending parallel to the ac crystallographic plane. Color code: Pb, cyan; N, blue; O, red; C, dark gray. (C) View along the c crystallographic axis, showing the weak π-π interactions between the aromatic rings of the phen molecules belonging to neighboring 2D layers. Figure 4:

(A) Partially labeled plot showing the coordination environment around the Pb(II) ion in 3. Hydrogen atoms have been omitted for clarity. Symmetry operations: ('): -x, -y, -0.5+z; (''): 0.5x, 0.5+y, z; ('''): x, 1-y, -0.5+z; (*): 0.5-x, -0.5+y, z; (**): x, -y, 0.5+z; (***): x, 1-y, 0.5+z. (B) Plot of the 2D network of 3 extending parallel to the bc plane.

Color code: Pb, cyan; S,

yellow; O, red; C, dark gray. Figure 5:

(A) Partially labeled plot showing the coordination environment around the Pb(II) ion, and the 8-membered and 16-membered macrometallocycles in the structure of 4. Hydrogen atoms have been omitted for clarity. Symmetry operations: ('): 1-x, -y, -z; (''): 1-x, 1-y,-z; (*): x, -1+y, z; (**): x, 1+y, z; (***): 1-x,2-y,-z. (B) 2D structure of 4 due to weak π-π interactions between the phen ligands of neighboring chains extending parallel to the bc crystallographic plane.

Figure 6:

13

C CPMAS NMR spectrum of 1 in the solid state.

Figure 7:

13


Figure 8:

13


Figure 9:

13




1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 48

32 Figure 10:

207

Pb MAS NMR spectrum of 1 (black) and simulated spectrum (red) in the solid-state. The

individual simulated spectra for Pb(1), Pb(2), and Pb(3) are also given in grey, purple, and green, respectively. Figure 11:

207

Pb CPMAS NMR spectrum of 2 (black) and simulated spectrum (red) in the solid state.

Figure 12:

207

Pb CPMAS NMR spectrum of 3 (black) and simulated spectrum (red) in the solid state.

Figure 13:

207

Pb CPMAS NMR spectrum of 4 (black) and simulated spectrum (red) in the solid state

Figure 14: TGA diagram of 2. Figure 15: Solid-state excitation spectra of (A) 1, (B) 2 at room temperature.


Page 33 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


33

Pb3***

Pb2&

A



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 48

34

B

C


Page 35 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


35

D

E Figure 1 ACS Paragon Plus Environment


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 48

36

A

B

C

D

Figure 2


Page 37 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


37

A

B

Figure 3

C



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 38 of 48

38

A

B

Figure 4


Page 39 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


39

A

B

ACS Paragon Plus Environment Figure 5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 40 of 48

40

C=O

200

ppm

CH2

150

100

50

0

Figure 6

1-10 phenanthroline

1,10-φαινανθρολίνη

CH2 C=O

ppm

200

150

100

Figure 7


50

0

Page 41 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


41

C=O

200

ppm

150

CH2

100

50

0

Figure 8

1,10-φαινανθρολίνη 1-10 phenanthroline

C=O

ppm

200

150

100

Figure 9


CH2

50

0


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 42 of 48

42

Figure 10

Figure 11 ACS Paragon Plus Environment

Page 43 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


43

Figure 12

Figure 13



44

100

Weight loss %

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 44 of 48

80

60 Compound 2

40

20 0

200

400

600 o

Temperature, T C

Figure 14


800

Page 45 of 48

45

Intensity

A

Compound 1

480

500

520

540

560

Wavelength, nm

Compound 2

B Intensity

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


500

550

600

Wavelength, nm

Figure 15


650


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 48

46

Scheme 1. Coordination modes of the oda (-2) and tda (-2) ligands in 1-4.


Page 47 of 48

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48


47

Pb(CH3COO)2, pH~3

Pb(CH3COO)2, pH~3

Pb(NO3)2, phen, pH~3

[Pb3(oda)3]n (1)

COOH

COOH

CH2

CH2

O

S

CH2

CH2

COOH

COOH

[Pb(tda)]n (3)

[Pb(phen)(tda)]n (4)

Pb(CH3COO)2, phen, NaOH,pH~8

[Pb(phen)(oda)]n (2)

Scheme 2 ACS Paragon Plus Environment

Pb(CH3COO)2, phen, pH~4


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 48 of 48

48

For Table of Contents Use Only Synopsis pH-Specific hydrothermal reactivity in Pb(II)-oda/phen and Pb(II)-tda/phen systems afforded the metalorganic hybrid polymers [Pb3(oda)3]n(1), [Pb(phen)(oda)]n(2), [Pb(tda)]n(3), and [Pb(phen)(tda)]n(4). 1-4 13

207

were characterized by elemental analysis, FT-IR, CP-MAS-( C,

Pb)-NMR, TGA-DTG, Luminescence,

and X-ray diffraction. O vs. S-ligands promote distinct lattice composition-dimensionality(2D-3D) changes at the binary and ternary level, bestowing spectroscopic fingerprint identity to Pb(II)-coordination and luminescence activity.

Synopsis Figure

2D

3D COOH

COOH CH2

3D

Pb(II)

CH2

O

S

CH2

CH2

COOH

COOH

N

N


2D

Binary and Ternary MetalâOrganic Hybrid Polymers in Aqueous Lead

Recommend Documents

Binary and Ternary MetalâOrganic Hybrid Polymers in Aqueous Lead