Substituent Influence on Structural and Luminescent Diversities of Cu3

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Substituent Influence on Structural and Luminescent Diversities of Cu3(pyrazolate)3-CunIn Coordination Supramolecular Isomers Shun-Ze Zhan, Tong Feng, Weigang Lu, Mohd. R. Razali, and Dan Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01476 • Publication Date (Web): 09 Nov 2018 Downloaded from http://pubs.acs.org on November 10, 2018

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Crystal Growth & Design

Substituent Influence on Structural and Luminescent Diversities of Cu3(pyrazolate)3-CunIn Coordination Supramolecular Isomers Shun-Ze Zhan,* † Tong Feng, † Weigang Lu, ‡ Mohd. R. Razali § and Dan Li*‡ †Department

of Chemistry and Key Laboratory for Preparation and Application of

Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063, P. R. China. ‡College

of Chemistry and Materials Science, Jinan University, Guangzhou 510632,

P. R. China. §School

of Chemical Sciences, Universiti Sains Malaysia, Minden, 11800, Penang,

Malaysia. *E-mail for S.Z. Z.: [email protected], D. L.: [email protected]

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ACS Paragon Plus Environment

Crystal Growth & Design 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

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ABSTRACT: Three photoluminescent isomeric complexes [Cu3(L4)3]2[CuI]2 (labeled as complexes 1, 2 and 3) were prepared from the same bifunctional organic ligand HL4 (3-(4-pyridyl)-5-methyl-1H-pyrazole) and CuI by careful manipulation of the reaction conditions. Planar trinuclear Cu3(L4)3 and CuI/Cu2I2 units are integrated via NCu coordination bonds into Cu3Pz3-CunIn systems (Pz = pyrazolate). Complex 1 is a discreet supramolecular aggregate via cooperative -acidbase (Cu3I) and CuCu interactions. Complexes 2 and 3 are 2-fold interpenetrated three-dimensional frameworks. The small size of CunIn (n = 1 or 2) units and structural diversities in such Cu3Pz3-CunIn systems were realized by preinstalling a methyl group on pyrazole at the 5-position of the ligand. The three complexes exhibit subtly different yellow emissions under UV irradiation in their solid states, originating from their respective triplet excited states of the supramolecular coordination luminophores. These results demonstrate that the structural and luminescent diversities of the Cu3Pz3-CunIn-based complexes can be regulated by substituents.

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1. Introduction Multinuclear copper(I)/silver(I)-based clusters have been widely used to construct photofunctional coordination materials in many fields such as lighting1, 2, sensing3-5, optical devices6, photocatalysis7-9, and other areas10,

11.

Among them, CuI-based

clusters12 have been extensively reported to show fascinating structural diversity from the well-known rhombic Cu2I26, 13-19 and cubic Cu4I420, 21-27 to poly-nuclear aggregates28 and even polymers29-31, depending on the nature of the ligands32,

33

and synthesis

procedures.23 Owing to the cuprophilicity, heavy atom effect, rich valence electrons of copper and iodine atoms, along with electronic effect of organic ligands, CuI-based clusters

show

striking

emission

behaviors

such

as

thermochromism

and

mechanochromism.20, 21-25 Trinuclear planar M3Pz3 (M = Cu(I), Ag(I) or Au(I), Pz = pyrazolate) chromophores,34-39 on another note, have also attracted much attention as they exhibit rich photophysical and photochemical properties thanks to the intra- and/or intermolecular CuCu interactions40, 41 and -acidbase interactions42, 43-45. For years, our group has been particularly interested in these two kinds of copper(I) cluster-based complexes and their interesting luminescence functions such as dual emission,

thermochromism,

mechanochromism,

and

ratiometric

temperature

sensing.45-50 CunIn and Cu3Pz3 can be integrated into one matrix by using appropriate bifunctional organic ligands51-54 such as (4-pyridyl)-pyrazole,46-49,

55

in which the

pyrazolate groups preferentially form Cu3Pz3 unit and 4-pyridyl subsequently coordinate to CunIn cluster (Scheme 1). On one hand, the two separated luminophores 3



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(CunIn and Cu3Pz3) may give off their individual characteristic emission colors as a dual emission system;46 while on the other hand, -acidsbase interactions between planar Cu3Pz3 and CunIn units dictate the formation of supramolecular -acidsbase adducts43, 47,

which may result in only one bright emission color instead. Previously, we reported a series of Cu3Pz3-CunIn-based (n = 4 or 3) luminescent

complexes constructed with bifunctional organic ligands 3-(4-pyridyl)-5-R-pyrazolate (L) (R = p-tolyl (L1), 2,4-dimethylphenyl(L2) or iso-butyl (L3)) (Scheme 1).46-49 They are assembled by trinuclear Cu3Pz3 and Cu4I4/Cu3I3 units through coordination of 4pyridyl to Cu4I4/Cu3I3 units. The size and geometry of CunIn can be controlled by R groups as well as the synthesis procedures, which will be discussed later in this paper. Different from the reported Cu3Pz3-CunXn (X = Cl, Br or I) analogues constructed with either the high-symmetry43, 55 or the elongated ligands3, Cu3L3 units reported here can adopt either cis- or trans-conformation (Scheme 1a) depending on the relative position of the pyridyl groups around Cu3 core in the Cu3L3 unit,34, 47 which lead to further structural diversity. In the Cu3Pz3-CunXn analogues, intertrimeric CuCu between Cu3Pz3 units46, 48, 49, 55 and -acidbase (Cu3I) interactions43, 45, 47 between Cu3Pz3 and CunXn units play important roles in stabilizing these supramolecular aggregates, resulting in interesting luminescence properties.

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Scheme 1. Schematic illustration of the construction of Cu3Pz3-CunIn systems (c) by [Cu3L3] units (cis- or trans- conformation) (a) and CunIn clusters (n = 4, 3, 2 or 1) (b). In this work, a smaller substituent (methyl group) was preinstalled on the 5-position of the pyrazole ring to further explore the substituent effects on the structure and luminescence properties of Cu3Pz3-CunIn-based complexes. Solvothermal reactions of 3-(4-pyridyl)-5-methyl-1H-pyrazole (HL4) with CuI under slightly different conditions in solvent and temperature afforded three isomeric complexes [Cu3(L4)3]2[CuI]2 (Scheme 2, Figure 1 and Figure S1 in the Supporting Information), in which planar trinuclear Cu3Pz3 and CuI/Cu2I2 units are integrated via NCu coordination bonds. Other supramolecular interactions such as -acidbase (Cu3I) and weak CuCu interactions are also presented cooperatively to form a discreet supramolecular aggregate (complex 1) or 2-fold interpenetrated three-dimensional (3-D) frameworks (complexes 2 and 3). All three complexes exhibit bright yellow emission color under UV irradiation in their solid states with subtle differences in excitation/emission 5



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profiles, microsecond-scale radiation lifetimes, and quantum yields, which can be attributed to the triplet excited states of the supramolecular coordination luminophores. These results demonstrate the successful control of the size and geometry of CunIn units from n = 1 to n = 4, as well as the structural diversities and luminescence properties in such Cu3Pz3-CunIn-based systems. 2. Experimental Section 2.1 Materials and methods Chemicals were purchased and used without further purification. Infrared spectra (IR) were performed on a Nicolet Avatar 360 FTIR spectrometer. 1H NMR spectroscopy was obtained on a Bruker DPX 400 spectrometer. All  values are given in ppm. C, H, and N analyses were performed on an Elementar Vario EL cube CHNS analyzer.

Thermogravimetric

(TG)

analyses

were

performed

on

a

Q50

thermogravimetric analyzer with a heating rate of 10 Cmin1 from room temperature to 800 C under a nitrogen flow (40 mLmin1). X-ray powder diffraction (XRPD) patterns were collected on a D8 Advance X-ray diffractometer with Cu K α radiation (

λ = 1.5406 Å). Photoluminescence spectra and lifetime data were collected on an Edinburgh FLS920 spectrometer equipped with a red-sensitive Peltier-cooled Hamamatsu R928P photomultiplier tube (PMT), a continuous Xe900 xenon lamp, a F900 microsecond flash lamp, and a closed cycle cryostat (Advanced Research Systems) with liquid helium as cooling media. Lifetime data were fitted with 6


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monoexponential-decay functions. In all cases, the crystalline samples were selected under a microscope. Their purity was assured by X-ray powder diffraction measurements (Figure S2 in the Supporting Information) and elemental analysis. 2.2 Synthetic procedures The ligand HL4 was synthesized according to our previous report47 with slightly modified procedure by using anhydrous acetone instead of 4-methyl-2-pentanone, producing HL4 as colorless block crystals (total yield: 52.1%). 1H NMR (400 MHz, CDCl3 with TMS as an internal standard) δ 8.65 (d, J = 6.1 Hz, 2H), 7.72 (d, J = 5.5 Hz, 2H), 6.51 (s, 1H), 2.42 (s, 3H). Complex 1: A mixture of CuI (19.1 mg, 0.1 mmol), HL4 (7.9 mg, 0.05 mmol), C2H5OH (1.0 mL), H2O (1.0 mL) and aqueous ammonia (40%, 0.15 mL) was sealed in an 8.0 mL Pyrex tube. It was heated in an oven at 180 C for 72 h, then cooled to room temperature slowly at a rate of 5 Ch-1. Light yellow block crystals were afforded (42% yield based on the ligand). IR (KBr, cm-1): 3453 (w), 3130 (w), 3017 (w), 2361 (w), 1689 (w), 1610 (w), 1552 (w), 1400 (vs), 1219(vs), 1144 (s), 1083 (m), 991 (s), 829 (m), 776 (m), 739 (m), 540 (m); elemental analysis calcd (%) for C27H24N9ICu4: C 37.87, H 2.81, N 14.73; found (%): C 37.82, H 2.84, N14.71. Complex 2: A mixture of CuI (19.1 mg, 0.1 mmol), HL4 (7.9 mg, 0.05 mmol), H2O (2.0 mL) and aqueous ammonia (40%, 0.15 mL) was sealed in an 8.0 mL Pyrex tube. It was heated in an oven at 160 C for 72 h, then cooled to room temperature slowly at 7



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a rate of 5 Ch-1. Light yellow block crystals were afforded (36% yield based on the ligand). IR (KBr, cm-1): 3451 (w), 3130 (w), 3015 (w), 2361 (w), 1689 (w), 1610 (w), 1552 (w), 1400 (vs), 1218 (vs), 1143 (s), 1083 (m), 991 (s), 829 (m), 776 (m), 739 (m), 540 (m); elemental analysis calcd (%) for C27H24N9ICu4: C 37.87, H 2.81, N 14.73; found (%): C 37.80, H 2.75, N 14.80. Complex 3: A mixture of CuI (19.1 mg, 0.1 mmol), HL4(7.9 mg, 0.05 mmol), H2O (2.0 mL) and aqueous ammonia (40%, 0.15 mL) was sealed in an 8.0 mL Pyrex tube. It was heated in an oven at 180 C for 72 h, then cooled to room temperature slowly at a rate of 5 Ch-1. Light yellow block crystals were afforded (48% yield based on the ligand). IR (KBr, cm-1): 3453 (w), 3132 (w), 3017 (w), 2361 (w), 1689 (w), 1610 (w), 1552 (w), 1400 (vs), 1219(vs), 1143 (s), 1083 (m), 991 (s), 829(m), 800 (m), 739 (m), 525 (m); elemental analysis calcd (%) for C54H48N18I2Cu8: C 37.87, H 2.81, N 14.73; found (%): C 37.90, H 2.78, N14.82. 2.3 X-ray crystallography Single crystal X-ray data for the complexes at 293.15 K were collected on an Oxford Diffraction Gemini E (Enhanced Mo X-Ray source, Kα, λ = 0.71073 Å) equipped with a graphite monochromator and ATLAS CCD detector (CrysAlis CCD, Oxford Diffraction Ltd). The data were processed using CrysAlis RED, Oxford Diffraction Ltd (CrysAlisPro 1.171.36.28, release 01-02-2013 CrysAlis171.NET).

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Crystal structures were solved by direct methods (SHELXTL-97) and refined by fullmatrix last-squares on F2 using SHELXTL-97.56 All non-hydrogen atoms were refined with anisotropic thermal parameters, and all hydrogen atoms were included in calculated positions and refined with isotropic thermal parameters riding on those of the parent atoms. Crystal data and structure refinements for the complex are summarized in Table 1. Selected bond lengths and angles are given in Tables S1-S2 in the Supporting Information. CCDC (1820450-1820452) contains the supplementary crystallographic data for this work. Table 1 Crystal data and structure refinements for the complexes. Parameter

Complex 1

Complex 2

Complex 3

Empirical formula

C27H24N9Cu4I

C27H24N9Cu4I

C54H48N18Cu8I2

Formula weight

855.61

855.61

1711.22

Temperature/K

293.15

293.15

293.15

Crystal system

triclinic

monoclinic

monoclinic

Space group

P-1

P21/c

C2/c

a (Å)

10.2701(15)

14.9831(12)

15.2268(18)

b (Å)

12.4618(19)

11.9168(10)

31.558(4)

c (Å)

12.9189(19)

17.6151(14)

24.744(3)

α (°)

106.076(2)

90.00

90.00

β (°)

107.466(2)

111.9110(10)

91.096(2)

γ (°)

100.158(2)

90.00

90.00

V (Å3)

1453.5(4)

2918.0(4)

11888(2)

Z

2

4

8

1.955

1.948

1.912

μ (mm-1)

3.984

3.969

3.897

F(000)

836.0

1672.0

6688.0

ρcalc

(g/cm3)

Crystal size

(mm3)

Reflections collected

0.18 × 0.14 × 0.13 0.24 × 0.2 × 0.15 0.18 × 0.13 × 0.12 10560

15901

42564 9



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Independent reflections

5085

5136

10449

Rint

0.0245

0.0246

0.0371

Rsigma

0.0362

0.0306

0.0344

5085/0/373

5136/0/373

10449/0/745

0.944

1.109

0.950

Final R indexes [I>=2σ (I)]

R1a = 0.0439 wR2b = 0.1225

R1a = 0.0303 wR2b = 0.0773

R1a = 0.0433 wR2b = 0.1168

Final R indexes [all data]

R1a = 0.0517 wR2b = 0.1294

R1a = 0.0385 wR2b = 0.0892

R1a = 0.0719 wR2b = 0.1479

Largest diff. peak/hole/e Å-3

1.50/-0.56

1.19/-0.41

1.62/-0.74

Data/restraints/parameters Goodness-of-fit on

a

3

F2

R1 = ∑(||Fo| - |Fc||)/∑|Fo|.

b

wR2 =[∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2.

Results and Discussion 3.1 Synthesis and physical characterization The three complexes were prepared by solvothermal reactions of HL4 and CuI under

slightly different conditions of solvent and temperature (Scheme 2). Small adjustments of synthesis conditions result in structural differences, indicating the formation of these isomers are both solvent and temperature dependent.57 Complex 1, a -acidbase adduct, was afforded by using ethanol/H2O as mixed solvent, similar to our previous report of the -acidbase adducts based on Cu3I3-Cu3(L3)3. However, single solvent (H2O) did not give such adducts. These results seem to reveal that ethanol is conducive to the formation of such -acidbase adducts. Compared with the reaction temperature (160 C) for preparing the complex 2, the higher reaction temperature (180 C) indicates that the complex 3 is probably a thermodynamic product. Small amount of NH3∙H2O is necessary as a base to deprotonate the ligand HL4.

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Scheme 2. Schematic illustration of preparation of the three isomers (left) and the crystal images under microscope (right). The three crystals appear to be different in morphology under microscope (Scheme 2). The PXRD patterns are consistent with the simulations of the corresponding single crystals, indicating high crystalline purities of the bulky samples. TG analyses imply that they are all stable up to 350 C (Figure S3 in the Supporting Information). 3.2 Structural description The three complexes are isomers of each other with the same chemical composition [Cu3(L4)3]2[CuI]2 (Figure 1), but different in the conformation of Cu3(L4)3 units, connecting modes between [CuI]2 and Cu3(L4)3 units, as well as supramolecular interactions.

11



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Figure 1. Perspective views of the complexes 1 (a), 2 (b) and 3 (c) with 50% thermal ellipsoid. Color codes: red, Cu; purple, I; blue, N; black, C; white cycle, H. In complex 1, the Cu3(L4)3 unit adopts a trans-conformation (Figure 1a) with two 4-pyridyl groups closely positioned to bind to two CuI units cooperatively (Figure 2), same as in our previous reports,47 leading to the formation of [Cu3(L4)3]2[CuI]2 coordination molecule. In the Cu3Pz3 unit, the NCu distances and NCuN angles are in good agreement with those in previously reported structures.46-49 Two CuI units are attracted to each other by weak CuCu (3.4361 Å) and ICu (3.7375 Å) interactions to form an elongated [CuI]2 parallelogram instead of a usual rhombus4. In the [CuIPy2]2 unit, the NCuN angles are of ca. 138.47, and the ICuN are 109.93 and 114.57, which topologically translated into a trigonal coordination geometry for the Cu atoms (Figure 2, Tables S1-S2 in the Supporting Information). This coordination mode is 12


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different from that in the complexes 2 and 3, which we believe is related to the interactions of the adjacent Cu3Pz3 units, as well as the conformation constraint in Cu3(L4) unit.

Figure 2. Structural diagram of the complex 1. (a) Molecular structure showing the coordination and composition of [Cu3(L4)3][CuI]2[Cu3(L4)3]. (b) Packing mode showing intermolecular Cu3I (-acidbase, green dotted line), CuCu (red dotted line) and CuI (green dotted line) interactions. (H atoms are omitted for clarity. Symmetry codes: A: -x+1; -y-1; z) These [Cu3(L4)3]2[CuI]2 coordination molecules are supported by intermolecular Cu3I (-acidbase) and CuCu interactions between Cu3(L4)3 and CuI units (Figure 2 and Figure S4 in the Supporting Information), as in previously reported structures.3, 43, 47

The distance between I atoms and the centre of Cu3 is about 2.6445 Å, and the

CuI distances are about 3.0132, 3.1961, and 3.3580 Å (Table S3 in the Supporting Information), the shortest one is similar to the previous reports.45,

47

The shortest

CuCu distance is 3.3718 Å, which is slightly longer than that in the reported 13



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Cu2I2(NH3)2-sandwiched Cu3(pyrazolate)3.45 A perpendicular instead of parallel packing mode is shown between [CuI]2 and Cu3 planes with a dihedral angle of ca. 95.20 (Figure 2), which is perhaps due to the large steric hindrance of pyridyl groups within the CuI units. Through such intermolecular Cu3I (-acidbase) and weak CuCu interactions, the CuIPy2 and Cu3Pz3 units are integrated together to form one Cu3Pz3[CuI]2Cu3Pz3 supramolecular aggregate, then extended into a polymeric chain and packed to form complex 1 (Figure 2 and Figure S4 in the Supporting Information). In complex 2, Cu3(L4)3 unit adopts a cis-conformation (Figure 1b). Rhombic Cu2I2 units connect these Cu3(L4)3 units in a classical Cu2I2Py4 mode to form a 2-dimensional layer-like structure (Figure 3a-b). Each Cu2I2 unit connects four Cu3(L4)3 units, and each Cu3(L4)3 unit connects two Cu2I2 units, leaving one 4-pyridyl group in every Cu3(L4)3 unit vacant in such a structure. The bond parameters in Cu2I2Py4 units are similar to those reported structures (Table S1 in the Supporting Information).6,

13-18

Interestingly, the vacant 4-pyridyl group in the Cu3(L4)3 unit further coordinate to one of the Cu atoms in another Cu3(L4)3 unit along b crystallography axis, leading to the formation of a 3-D framework (Figure 3c-e). As shown in Figure 3, the NCu distance is about 2.244(1) Å, much longer than the normal NCu distance, and the N(Pz)CuN(Pz) angle is about 164.6(1), as reported in our previous report.47 The NCu weak coordination interactions connect these Cu3(L4)3 units to form 21 helical chains (left- and right-handed, Figure 3d-e) along b axis. The two chiral chains are 14


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linked by Cu2I2 units independently to form two separated chiral 3-D networks, which are penetrating each other through centrosymmetrical operation, leading to a mesomeric 2-fold interpenetration (Figure S5 in the Supporting Information). Careful examination within the structure found that the classical chair stacking conformation presents with intertrimeric CuCu distance of ca. 3.667(2) Å (Figure S5a in the Supporting Information), much longer than that in those Cu3Pz3 analogues with similar chair-like stacking modes,34, 36, 55 indicating a rather weak CuCu interaction.

Figure 3. Structural diagram of complex 2. (a, b) Connecting modes between [Cu3(L4)3] and [Cu2I2] to show a 2-D layer-like structure. (c-e) Connecting modes via

15



Page 16 of 40

weak CuN interactions between [Cu3(L4)3] to show a left- (d) and right-handed (e) helical chain. (H atoms are omitted for clarity) Topological analysis58 was performed to simplify the complicated 2-foldinterpenetrated 3-D structure. Each Cu2I2 unit acts as a planar 4-connected node to connect four different Cu3(L4)3 units, while each Cu3(L4)3 unit represents a tetrahedral 4-connected node to connect two Cu2I2 units and two adjacent Cu3(L4)3 units, leading to a binodal topological network with point symbol (66)2(6482) and vertex symbol (66666262)2(626262628484) (Figure 4 and Figure S5f-g), which reveals that the 6membered ring is the smallest one. There are several topology nets reported showing both tetrahedral and square planar nodes in a ratio of 2:1, however, with 4-membered ring being the smallest.58, 59

Figure 4. Topological representation of the complex 2. (a) Simplification diagram showing planar (purple ball, Cu2I2 unit) and tetrahedral (red ball, Cu3(L4)3 unit) 4connected nodes. (b) Single 3-D topological network showing point symbol (66)2(6482). 16


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Compared with the two complexes discussed above, complex 3 shows an asymmetrical building unit composed of two cis-Cu3(L4)3 units and one Cu2I2 unit (Figure 1c). Like the complex 2, each Cu2I2 unit connects four Cu3(L4)3 units with Cu atoms adopting tetrahedral coordination geometry, and each Cu3(L4)3 unit connects two Cu2I2 units (Figure 5a). The third residual N-pyridyl in Cu3(L4)3 unit is vacant, same as the complex 1 but different from the complex 2. For the Cu3(L4)3 unit, due to lack of attractions between I atom and N-pyridyl group, the N(Pz)CuN(Pz) angle (larger than 175 ) is much closer to an ideal linear coordination mode (Table S2 in the Supporting Information). The Cu3(L4)3 and Cu2I2 units are connected to form a 3-D network with a dia topology58 with Cu2I2 units acting as tetrahedral 4-connected nodes and Cu3(L4)3 units as linear linkers (Figure 5 and Figure S6 in the Supporting Information). The large void allows the formation of the 2-fold interpenetrated network. Critical examination on the structure found that the multiple intertrimeric stacking modes present among the Cu3Pz3 units with intertrimeric CuCu distances ranging from 3.259(3) to 4.050(3) Å (Table S2 and Figure S6a-d in the Supporting Information), indicating weak CuCu interactions.

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Figure 5. Structural diagram of complex 3. (a) Connecting modes between [Cu3(L4)3] and [Cu2I2]. (b, c) illustration of 1-D {[Cu3(L4)3]Cu}n chains connected by I atoms to form 3-D structure. (d) 2-fold interpenetrated dia topological network with Cu2I2 as a tetrahedral 4-connected node (purple ball). (H atoms are omitted for clarity. Symmetry codes: A: x; -y-1; z-0.5; B: x+0.5; -y-0.5; z+0.5) 3.3 Structural diversities As previously reported, pyrazolate groups in the (4-pyridyl)-pyrazolate ligands in this work are highly selective to form classical planar trinuclear Cu3Pz3 units.46-49 The [CuI]2 units are then bonded to the residual N-pyridyl atoms to form Cu3Pz3-CunIn complexes. The slight variations in synthesis conditions lead to different conformations of Cu3(L4)3 units and supramolecular interactions between these clusters, resulting in 18


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three isomers. However, the exact mechanism under these conditions for the formation of these isomers is yet to be explored. The CunIn units show a wide variety of coordination geometry (0D, 1D, 2D, and 3D) and size (n ≥ 1),12 depending on the organic ligands used and synthesis procedures. We have systematically demonstrated the control of the size and geometry of CunIn units by changing the substituents from methyl, iso-butyl,47 to 2, 4-dimethylphenyl/p-tolyl, 46, 48, 49

as in ligands L4, L3, L2/L1, respectively (Scheme 1). These results indicate that

the size and geometrical shape of the substituent plays an important role in controlling the size and geometry of CunIn units. For ligands L1 and L2, the p-tolyl and 2, 4-dimethylphenyl groups are bulky, and the strong conjugation effects enhance their rigidities of ligands, which further increase the steric effects. Therefore, the resulted Cu3Pz3-Cu4I4 complexes show similar 2-D layer structures guided by C3 symmetry.46, 48, 49 Subtle structural diversities lie in the packing modes between the layers depending on the synthesis procedures (direct or postsynthetic solvent-assisted reactions) and auxiliary terminal ligands (NH3, NH2CH3, CH3CN, pyridine, pyrazine, 1,4-diazabicyclo[2.2.2]octane, and triphenylphosphine).46, 48, 49

In the ligand L3, iso-butyl group is also very bulky, however, the steric effect is

weakened as a result of its flexibility to some extent, leading to two isomeric Cu3Pz3Cu3I3-based complexes supported by intermolecular Cu3I (-acidbase) and weak CuCu interactions.47

19



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In this work, a methyl group, the smallest substituent used by this far, provides a loose space around Cu3(L4)3 units compared to the complexes derived from L1-L3, which subsequently allows the formation of various structural morphology such as acidbase adducts in the complex 1 and interpenetration in the complexes 2 and 3. The trans-conformation of Cu3(L4)3 unit presents a short spatial distance between the two 4-pyridyl groups in a Cu3(L4)3 unit, which renders them to be able to bind to one CunIn unit synergistically as a bidentate chelating metalloligand.54 On the other hand, the cisconformation of Cu3(L4)3 unit acts as a potential tridentate metalloligand with larger geometrical shape, facilitating the formation of interpenetrated 3-D network, which enriches the structural diversity. 3.4 Luminescence properties Under ambient conditions, the bulk crystal samples of complexes 1-3 show light yellow color (Figure S1 in the Supporting Information). Their solid UV-Vis absorbance spectra display a broad absorbance band covering from 250 nm to 480 nm with two strong absorbance bands at about 250  300 nm and 350  400 nm companied by a weak tail band from 400 nm to 480 nm (Figure S7 in the Supporting Information), which is consistent with their yellow color under natural light. Similar absorption above 350 nm was reported in these rhombic Cu2I2-based complexes by Li’s group6 and it was assigned to the transition from Cu and I atoms in Cu2I2 unit to * of organic ligand (MLCT and XLCT).

20


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Photoluminescence spectra show that all the isomers present a broad and structureless emission band from 500 nm to 650 nm (emmax = 560  565 nm) with a weak tail band to 700 nm upon excitation at 370 nm (Figure 6 and Figure S8 in the Supporting Information), and the quantum yields (Table 2, QY) were calculated to be 25.7%, 29.3% and 25.8% for the complexes 1, 2 and 3, respectively. Monitored with the optimal emission maxima, complexes 1 and 2 show very broad excitations from 250 nm to 450 nm with two excitation peaks at about 275 nm and 370 nm, while the complex 3 shows a weak excitation band from 250 nm to 300 nm and a broad but strong excitation band from 300 nm to 500 nm (Figure S9 in the Supporting Information). The excitation spectra profiles of all the three complexes are similar with those reported for Cu3Pz3-Cu3I3 analogues,47 which are covered by their UV-Vis absorbance spectra. Whether excited at 275 nm or 370 nm, all the three isomers show very similar emission profiles with emmax at 560  565 nm, indicating the emissions are probably originated from excited states of similar energy. However, the emission intensity upon 370 nm excitation is much stronger than 275 nm excitation, indicating lower energy excitation (370 nm) is the optimal excitation (Figure S8 in the Supporting Information). Table 2 Selected photoluminescence data upon 370 nm excitation for the complexes 13 from 300 K to 30 K. Temperature Parameters

300 K emmax (nm)

 (s)

100 K QY(%)

emmax (nm)

 (s)

30 K emmax (nm)

 (s) 21



Page 22 of 40

1

565

15.24

25.7

565

26.39

565

19.73

2

565

9.06

29.3

565

41.21

565

34.13

3

560

12.29

25.8

560

27.18

560

27.49

To further explore the photoluminescence properties and their emission origination, temperature-dependent luminescence properties including decay lifetime for these isomers were performed from 300 K to 30 K (Figure 6 and Figures S9-16 in the Supporting Information). Selected data were summarized in Table 2 and Table S5 in

the Supporting Information.

Figure 6. Temperature-dependent photoluminescence spectra of the complexes 1 (a), 2 (b) and 3 (c) in solid state. The insets are the photographs of the crystal samples exposed under 365 nm UV lamp at ambient temperature. With temperature decreasing from 300 K to 30 K, the emission intensities of these isomers increased dramatically about 3 times for complexes 1 and 3, and 10 times for complex 2 (Figure 6). Normalized emission spectra under different temperatures show 22


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no obvious shifting in max (Figures S12-13 in the Supporting Information). Similar variation tendency was observed for 275 nm excitation (Figure S11 in the Supporting Information). The decay profiles for the isomers were fitted well with a monoexponential curve at measured temperatures. With temperature decreasing from 300 K to 30 K, the lifetime increased from 1015 s to 3040 s (Figures S1416 in the Supporting Information). These data indicate that the emissions can be ascribed to phosphorescence. The increased lifetime and emission intensity under lower temperature are caused by the decreasing of non-irradiation decay. The origination of photoluminescence emissive behaviors for the isomers is worth to be discussed in detail. As to those reported similar complexes, two coordination luminophores are incorporated into each individual isomer, which provides a possibility of dual emission based on these two luminophores. In the Cu3Pz3-Cu4I4 system46, 48, 49, the large distance of the two luminophores [Cu3Pz3]2 and Cu4I4 in space allows of dual emissive behaviors, and intertrimeric CuCu interaction in the staggered [Cu3Pz3]2 dimeric units can further regulate these dual emissive behaviors.48 However, no distinct dual emissive behaviors were observed in the Cu3Pz3-Cu3I3 system,47 due to the formation of one supramolecular luminophore (Cu3I3–Cu3Pz3–Cu3Pz3–Cu3I3 or Cu3Pz3–Cu3I3–Cu3Pz3) supported by -acidbase (Cu3I) and CuCu interactions, which results in only one dominant emission band. It is plausible that the integration of the two luminophores leads to the emerging of a new supramolecular luminophore and the disappearing of the characteristic emission of each individual luminophore. 23



In this work, the CuIPy2 and Cu3Pz3 units in the complex 1 are integrated to form one Cu3Pz3[CuI]2Cu3Pz3 supramolecular luminophore by -acidbase (Cu3Pz3I) and CuCu interactions. In the complexes 2 and 3, the two coordination luminophores, Cu2I2Py4 and [Cu3Pz3]2/[Cu3Pz3]n, are well separated in space. However, it is surprising to see that only one dominant emission band presents for complexes 2 and 3, which indicates one luminophore dominates the radiation decay in each complex. Therefore, it is reasonable that complex 1 shows only one dominant emission band since it contains only one integrated Cu3Pz3[CuI]2Cu3Pz3 supramolecular luminophore. This can probably be ascribed to a triplet cluster-centered (3CC) excited state, dominated by the contribution of halide-to-metal charge transfer (3XMCT) with a minor contribution of halide-to-ligand charge transfer (3XLCT), similar to those reported previously.43, 45, 47 However, the other two isomers with two well separated Cu2I2Py4 and [Cu3Pz3]2/[Cu3Pz3]n luminophores exhibit only one dominant emission band with emission maxima similar to the complex 1. This is different from the Cu3Pz3Cu4I4 system, in which two separated luminophores lead to dual emissive behaviors. Numerous literature have reported the structures and photoluminescence properties of Cu3Pz3 systems, most of which exhibit intertrimeric CuCu interaction, leading to color emission from yellow to red with emmax at 550  750 nm based on 3CC highly dependent on the stacking modes and intertrimeric CuCu distances.34-36, 50, 55 Careful investigation into the excitation profiles of these complexes suggests that the optimal excitation maxima lie within the higher energy (HE) band (ex = 250  320 nm) and 24


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not the lower energy (LE) band (ex = 320  420 nm) (Table S4 in the Supporting Information). Theoretical calculation by Cundari in 2006 implied that the excitation wavelength (ex(av)  270  30 nm) is less sensitive to metals, substituents and stacking modes.35 However, a very few examples reported that LE excitation (ex = 320  420 nm) can induce the characteristic emission (LE band, 650  700 nm) based on excimeric [Cu3Pz3]2 luminophore,46 due to the dynamic interplay between [Cu3Pz3]2 and another luminophores such as CunIn46,

48

as well as the conjugated organic

chromophore36, 61, which usually show the optimal excitation in LE band (ex = 320  420 nm). In this work, the complexes 2 and 3 have the same Cu2I2 luminophores but the [Cu3Pz3]2/[Cu3Pz3]n luminophores are different in stacking modes and intertrimeric CuCu distances. They show similar excitation and emission profiles, and their optimal excitations lie in LE band (ex > 350 nm), which is more related to the population of CunIn than [Cu3Pz3]2/[Cu3Pz3]n luminophore. Accordingly, the effective emissions maybe originate from Cu2I2 luminophore and can be attributed to the triplet clustercentered (3CC) excited state of Cu2I2 unit with a combination of iodide-to-copper charge transfer (3XMCT) and halide-to-ligand charge transfer (3XLCT).17 It is also supported by Li and coworkers’ report in which they postulated that the photoluminescence properties of the Cu2I2-based phosphors can be regulated by tuning the LUMO energies of ligands.6 The complexes 2 and 3 are constructed with the similar Cu2I2 luminophore and the same organic ligand. 25



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The intertrimeric CuCu distances in these reported chair-like stacking dimeric [Cu3Pz3]2 complexes are usually in the range of 2.90  3.50 Å (Table S4 in the Supporting Information), which is responsible for the bright luminescence. However, the complex 2 presents much longer intertrimeric CuCu distance (3.667(2) Å) than those reported, implying an insignificant intertrimeric cuprophilicity as cuprophilic interaction dies off rapidly as a function of CuCu distance (approximately r-6 dependence).40 Therefore, it is reasonable that the emission originated from Cu2I2 luminophore was observed in the complex 2.

However, the complex 3 shows much shorter intertrimeric CuCu distances (3.259(3) Å and 3.333(6) Å) in a chair-like stacking geometry than that in the complex 2. These CuCu distances are longer than the sum of the van der Waals radii (2.8 Å) of two Cu atoms,62 but still within the range of cuprophilicity and similar to the distances in other chair-like stacking [Cu3Pz3]2 analogues. Therefore, the contribution of [Cu3Pz3]2 units to its emission should not be neglected. Upon LE excitation (ex = 370 nm), the possible dynamic interplay between Cu2I2 and [Cu3Pz3]2 units maybe lead to the population of the excited state of [Cu3Pz3]2 to induce its emission. However, no distinguishable emission bands originating from Cu2I2 and [Cu3Pz3]2 were observed because of their extensively overlapped emission profiles as well as the limitation of the current physical measurement capacity of our lab. 4 Conclusions

26


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In conclusion, three photoluminescent coordination supramolecular isomers based on [CuI]2 and Cu3Pz3 units were prepared in a solvothermal condition. The CuI/Cu2I2 units are achieved in this work by judiciously installing a small substituent (methyl group) on pyrazole moiety of the ligand. Subtle variations of the synthesis condition lead to the formation of the three isomers that show weak but different supramolecular interactions between the two coordination luminophores. While the complex 1 is a Cu3Pz3[CuI]2Cu3Pz3 (-acidbase) adduct, the complexes 2 and 3 are 2-fold interpenetrated 3-D networks composed of Cu2I2 and Cu3Pz3 units that are well separated in space. The three isomers exhibit similar phosphorescence emission properties originating from the triplet excited states of the supramolecular coordination luminophores. These results demonstrate a successful control of the size and geometry of CunIn units from n = 1 to n = 4, as well as the structural diversities and luminescence properties in such Cu3Pz3-CunIn-based systems, providing a new insight into exploring structure-luminescence relationships in the Cu3Pz3-CunIn system. Further studies on the nature of the photophysical process in such a system are ongoing. ASSOCIATED CONTENT Supporting Information. Crystal data (CIF files), additional physical measurements and structural analysis. This material is available free of charge via the Internet at http://pubs.acs.org. Access Codes 27



Page 28 of 40

CCDC 1820450-1820452 contain the supplementary crystallographic data for this paper.

These

data

can

be

obtained

free

of

charge

via

www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. AUTHOR INFORMATION Corresponding Author * E-mail for Shun-Ze Zhan: [email protected] Dan Li: [email protected] ORCID Dan Li: 0000-0002-4936-4599 Shun-Ze Zhan: 0000-0002-9152-6192 Weigang Lu: 0000-0001-9751-8241 Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was financially supported by the National Natural Science Foundation of China (Nos. 21731002, 21471094, and 91222202) and the Guangdong Natural Science Foundation (No. 2014A030313477). REFERENCES 28


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For Table of Contents Use Only Title: Substituent Influence on Structural and Luminescent Diversities of Cu3(pyrazolate)3-CunIn Coordination Supramolecular Isomers Authors: Shun-Ze Zhan,* Tong Feng, Weigang Lu, Mohd. R. Razali and Dan Li* TOC graphic

SYNOPSIS

Three photoluminescent isomeric complexes [Cu3(L4)3]2[CuI]2 (labeled as complexes 1, 2 and 3, L4 = 3-(4-pyridyl)-5-methyl-pyrazolate) were reported. The size of CunIn (n = 1  4) units and structural diversities in such Cu3Pz3-CunIn systems were realized by preinstalling different-sized substituents on pyrazole moiety of the ligand, demonstrating a successful regulation of structural and luminescent diversities in the Cu3Pz3-CunIn-based complexes.

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Substituent Influence on Structural and Luminescent Diversities of Cu3

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