Zn[Htma][ddm]: An Interesting Three ... - American Chemical Society

Dec 11, 2009 - Institute of Materials Physical Chemistry, Huaqiao University, Quanzhou, Fujian 362021, China,. ‡State Key Laboratory of Structural C...
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DOI: 10.1021/cg901259e

Zn[Htma][ddm]: An Interesting Three-Dimensional Chiral Nonlinear Optical-Active Zinc-Trimesate Framework†

2010, Vol. 10 930–936

Li Liu,# Shu-Ping Huang,‡ Guo-Dong Yang,# Hao Zhang,‡ Xiao-Li Wang,# Zhi-Yong Fu,§ and Jing-Cao Dai*,# #

Institute of Materials Physical Chemistry, Huaqiao University, Quanzhou, Fujian 362021, China, State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, and §College of Chemistry, South China University of Technology, Guangzhou, Guangdong 510640, China

‡

Received October 10, 2009; Revised Manuscript Received November 15, 2009

ABSTRACT: The three-dimensional (3D) chiral helical framework of the new polymeric solid, Zn[Htma][ddm] (1) (tma = trimesate, ddm = p,p0 -diamino-diphenyl-methane), has been prepared by the hydrothermal reaction of zinc acetate dihydrate, H3tma, and ddm. X-ray single-crystal structural analysis reveals that 1 (C22H18N2O6Zn) crystallizes in the orthorhombic P212121 space group, Z = 4 (a = 5.4533(3) A˚, b = 17.593(1) A˚, c = 20.542(1) A˚, V = 1970.8(2) A˚3). Tetrahedrally coordinated zinc centers in 1 bridged by the rigid trigonal tectonic tma ligands with Δ-configuration plus the flexible ddm molecules give rise to an interesting 3D chiral helical diamondoid network single enantiomer that has been confirmed by solid-state circular dichroism spectra. 1 is stable up to about 297 °C in the ambient environment and exhibits an intense fluorescent emission band at 420 nm upon excitation at 326 nm and the band gap semiconducing character. The theoretical calculations reveal that 1 is a potential nonlinear optical-active material.

Introduction Second-order nonlinear optical (NLO) crystalline solids represent an important functional material that has been widely used in the photonic technologies.1 The most popular technologically NLO materials are inorganic borates and phosphates.2 The most obvious feature for these NLO materials is the strictly requirement of intrinsically acentric or chiral arrays in either crystal structures or bulk solids. On the other hand, rapid growth in the field of supramolecular coordination polymer chemistry provides a robust bridge for the intriguing structural diversities connecting the new functional materials.3-5 Even though many interesting polymeric solids with unprecedented architectures and fascinating topologies as well as novel functionality have been reported, as two-dimensional (2D) networks in 4-linked square grid (4,4),6 3-linked brickwall,6a,7 herringbone,8 honeycomb (6,3) networks9 or bilayers,6l,10 three-dimensional (3D) frameworks in diamondoid,11 primitive cubic (R-Po net),6k,12 honeycomblike6k,13 and other frameworks,6k,13a,14 the design and synthesis of polymeric crystalline solids with acentric and chiral, and in particular chiral helical, frameworks are still interesting topics and represent a significant challenging task15 in the coordination polymeric chemistry. Not only are they expected to find potential NLO applications,16 but also these chiral helical frameworks may be linked to analogous models for the study biological DNA chains and pharmacological helical compounds.17 The popular promising approach for the fabrication of acentric and chiral polymeric frameworks is usually based upon the spontaneous reactions of metal centers with unsymmertrical or chiral bridging ligands, such as isophthalate,16f imidazole 4,5-dicarboxylate,15c † This article is dedicated to Professor Xin-Tao Wu on the occasion of his 70th birthday. *Author to whom correspondence should be addressed. E-mail: [email protected].

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terephthaloylmonoalanine,15f 3,5-bis(2-pyridyl)pyrazole,15g 4-(1H-1,2,4-triazol-3-yl)-4H-1,2,4-triazole,15e terakis[4-(carboxyphenyl)oxamethyl]methane acid,16e and pyridinecarboxylates, etc.1e,18 However, in contrast to an unsymmetrical ligand route, comparatively few such frameworks have been observed in the fabrication from complete symmetrical organic ligands.19 As a part of our continuing efforts in the exploratory design and synthesis of functional crystalline solids with mineralominetic architectures,20 our recently initiated explorations of a symmetrical organic ligand approach have led to a new 3D chiral helical NLO-active polymeric framework analogous to potassium dihydrogen phosphate KDP (KH2PO4) topological structure, Zn[Htma][ddm] (1) (tma = trimesate, ddm = p,p0 -diamino-diphenyl-methane), of which we herein report its synthesis, structure, characteristics, and electronic structure and optical property calculations. Experimental Section All chemicals were commercially purchased from Acros Chemical Co. and used as received without further purification. Infrared spectra were recorded on Nicolet Nexus 470 spectrometer using KBr pellets, and the C, H, N, and O elemental microanalyses were carried out with a Vario EL III elemental analyzer. Powder X-ray diffraction (XRD) patterns were collected on a Bruker AXS D8Advanced diffractometer at 40 kV, 40 mA with Cu KR (λ = 1.5406 A˚) radiation with a scan speed of 5° 3 min-1 and a step size of 0.1° in 2θ. Fluorescent data were recorded on an Edinburgh FL-FS920 TCSPC system, and thermal gravimetric analysis (TGA) was performed with a heating rate of 10 °C 3 min-1 using a TA5200/ MDSC2910 system. Solid-state circular dichroism (CD) spectra were collected on a JASCO J-810 spectrometer with 4 nm spectral slit width using KCl pellets, and optical diffuse reflectance spectrum was carried out on a Shimadzu UV2550 spectrometer equipped with ISR2200 integral sphere using a BaSO4 plate as a 100% reflectance standard at room temperature. Synthesis. The title compound was synthesized hydrothermally in a 25 mL Parr Teflon-lined stainless steel reaction vessel under r 2009 American Chemical Society

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Table 1. Some Crystal, Data Collection and Structure Refinement Parameters for 1 compound

1

empirical formula C22H18N2O6Zn formula weight 471.75 crystal system orthorhombic space group P212121 (No 19) a (A˚) 5.4533(3) b (A˚) 17.593(1) c (A˚) 20.542(1) 1970.8(2) V (A˚3) Z 4 T (K) 293(2) 1.291 μ (mm-1) 1.590 dcalcd (g 3 cm-3) λ (Mo-KR) (A˚) 0.71073 collected reflections 15026 independent reflections 4486 observed reflections 3930 (>2σ(I)) Flack parameter 0.01(2) 0.0353 Rint 0.0376 (for obs) R1 a 0.0857 (for obs) wR2b -3 ˚ 0.331/-0.509 largest diff peak/hole (e 3 A ) P P P P a b R1 = (||Fo| - |Fc||)/ |Fo|. wR2 = { w[(Fo2 - Fc2)2]/ w[(Fo2)2]}1/2, w = 1/[σ2(Fo2) þ (aP)2 þ bP], where P = (Fo2 þ 2Fc2)/3].

autogenous pressure. The static reaction of zinc acetate dihydrate (98.7 mg, 0.5 mmol), H3tma (63 mg, 0.3 mmol), ddm (89.2 mg, 0.5 mmol), and water (5 mL) in a molar ratio of 1.5:1:1.5:927 was allowed to heat at 130 °C for 4 days, and then was annealed at a rate of ca. 2 °C 3 h-1 to give about a 29% yield (41 mg, 0.09 mmol; based on H3tma used) of 1 as brown block-like crystals, which were collected by hand and washed with water and absolute alcohol. The yield of 1 can be increased up to ∼85% by the same reaction using the stoichiometric ratio of 1:1:1:618 instead of the above 1.5:1:1.5:927. C22H18N2O6Zn (471.75): Anal. Calcd. (found): H, 3.85 (3.93); C, 56.01 (56.06); N, 5.94 (5.87); O, 20.35 (20.10) %. IR (KBr pellet, cm-1): 3324 (w), 3241 (m), 2909 (w), 1908 (w), 1867 (w), 1689 (s), 1635 (s), 1617 (m), 1582 (m), 1508 (s), 1445 (w), 1434 (m), 1415 (w), 1344 (s), 1318 (w), 1241 (m), 1231 (w), 1186 (m), 1098 (m), 1065 (w), 1035 (s), 930 (w), 860 (w), 820 (s), 748 (m), 671 (s), 640 (m), 580 (m), 522 (m). Structure Determinations. Single crystal of the title compound suitable for data collection, with approximate dimensions of 0.20  0.20  0.18 mm, was selected for X-ray structure measurement. Data collections for 1 were performed on a computer-controlled Rigaku Mercury CCD diffractometer equipped with graphitemonochromated Mo KR radiation (λ = 0.71073 A˚) at 293 K. Empirical absorption corrections were applied for all of the data sets that were made with the Multiscan program.21 The structure was solved by direct methods using SHELXS-97 and refined by full-matrix least-squares techniques using SHELXL-97.22 All nonhydrogen atoms were treated anisotropically. The positions of hydrogen atoms were generated geometrically, except for the protonated carboxylate hydrogen atom (H6b) of tma ligand which was located from difference map and refined isotropically. Final refinements converged at R1 = 0.0376 for 1. Some crystallographic data are summarized in Table 1, and the selected bond lengths and bond angles of the title compound are listed in Table 2. More details on crystallographic information, as well as refinement data and anisotropic displacement parameters, are in the Supporting Information. Theoretical Calculation. In order to understand the relation between structure and properties better, band structure and optical property calculations were performed for the title compound based upon the crystallographic data of 1 by using the total-energy code CASTEP, which employs pseudopotentials to describe electronion interactions and represents electronic wave functions using a plane-wave basis set.23 The total energy was calculated by density functional theory (DFT) within the framework of nonlocal gradient-corrected approximations [Perdew-Burke-Ernzerhof (PBE)].24 The interactions between the ionic cores and the electrons were described by the norm-conserving pseudopotential.25 The

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Table 2. Selected Bond Lengths [A˚] and Angles [°] for 1a Zn-O1 Zn-O3(a) O1-Zn-O3(a) O1-Zn-N1 O3(a)-Zn-N1

1.934(2) 1.942(2) 121.3(1) 103.23(9) 110.8(1)

Zn-N1 Zn-N2(b) O1-Zn-N2(b) O3(a)-Zn-N2(b) N1-Zn-N2(b)

2.035(2) 2.085(3) 109.6(1) 100.1(1) 112.0(1)

a Symmetry transformations used to generate equivalent atoms for 1: a -x þ 4, y - 1/2, -z þ 3/2; b -x þ 7/2, -y þ 1, z - 1/2.

following orbital electrons were treated as valence electrons: C 2s22p2, H 1s1, N 2s22p3, O 2s22p4, and Zn 3d104s2. Considering the balance of the computational cost and precision, we chose a cutoff energy of 550 eV and a 5  1  1 Monkhorst-Pack k-point set mesh. It is important to include a significant number of empty bands when calculating optical properties. The exact number required will depend on the nature and the size of the system under consideration, and 72 empty bands were used in the calculations of optical properties. Otherwise parameters used in the calculations and convergence criteria were the default values of CASTEP code.

Results and Discussion Synthesis and Characterization. Title compound, formulated as Zn[Htma][ddm] (1), judging from the elemental analysis data and the refined structures, can be easily obtained in high yield (∼85%) by the hydrothermal reactions from a 1:1:1 stoichiometric proportion of zinc acetate dihydrate/H3tma/ddm. However, attempts to prepare any framework polymeric architecture by substitution of zinc center with cadmium atom, or tma ligand with isophthalate molecule, near an analogous phase of compound 1 have not yet succeeded. This compound is stable in air at ambient temperature and is almost insoluble in common solvents such as water, alcohol, and acetone. TGA trace of 1 shows an obvious weight loss starting at about 297 °C, and full decomposition of compound occurred at about 603 °C (Figure S1, see Supporting Information). The thermal stability of 1 has been also confirmed by powder X-ray diffraction pattern (Figure S2). The IR spectrum of 1 (Figure S3) shows the characteristic bands of the carboxylate groups of tma ligand in the usual region at 1344 cm-1 for the symmertric vibration and 1508 cm-1 for the asymmertric vibration. The bands at 3324, 3241, 2909, 1635, 1617, 1582, 1231, 1186, 1098, 1065, 1035, 930, 860, 820, 748, 671 cm-1 confirm the presence of ddm and tma ligands. Moreover, the band at 1689 cm-1 attributed to the protonated carboxylate group reflects that the incomplete deprotonation of H3tma upon the reactions with zinc ions occurred in the title compound. In addition, the solid-state CD spectrum (Figure S4) shows two strong exciton bands around 261 and 292 nm in the UV region that can be assigned to the absorbance of the π-π* charge-transfer transitions of the benzene rings and amino groups on the tma and ddm ligands, respectively, and the negative CD signal suggests that 1 is a right-handed helical single enantiomer.26 These are in good agreement with the structure of the title compound. Structure. X-ray single-crystal analysis reveals that the crystal structure of 1 is a 3D chiral helical framework crystallized in the P212121 space group, whose local coordination environment around the metal centers is depicted in Figure 1. The building unit of 1 is composed of a 4-coordinated zinc center, a tma ligand, and a ddm ligand, in which each 4coordinated zinc center is in a little distorted tetrahedral coordination environment [tetrahedral angle within 100.1(1)121.3(1)°], bonded by two bridging tma ligands and two bridging ddm molecules through two unidentate carboxylate

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Figure 1. The local coordination environment around the Zn centers in 1; the hydrogen atoms are omitted for clarity. Symmetry code: (a) -x þ 4, y - 1/2, -z þ 3/2; (b) - x þ 7/2, -y þ 1, z - 1/2; (c) -x þ 7/2, -y þ 1, z þ 1/2; (d) -x þ 4, y þ 1/2, -z þ 3/2.

groups [O1 and O3(a)] and two nitrogen donors [N1 and N2(b)]. The average Zn-O bond distance is 1.94 A˚ within a range of 1.934(2)-1.942(2) A˚, while the average Zn-N bond lengths are 2.06 A˚, and range from 2.035(2) to 2.085(3) A˚; all lie within a reasonable range as estimated from crystallographically determined bond lengths of a Zn-O or Zn-N single bond. On the other hand, either the tma or ddm molecule is bridged to two different zinc centers, of which the tma molecules provide the structural chirality for whole polymeric framework. Because two unidentate carboxylate groups in the tma molecule are twisted with Δ-configuration, the dihedral angle between these two carboxylate groups is 21.72°. And the tma ligands are bridged alternatively by zinc centers to generate a 1D “right-hand-helical Zn-tma chain” with a 17.6 A˚ of helical pitch along the [010] view (Figure 2a). Moreover, the neighboring 1D helical Zn-tma chains are parallel in inverse arrays that are further linked to each other by ddm spacers in two directions to construct a 3D noninterpenetrating framework (Figure 2b). Thus, the structural chirality of tma ligand can be transferred through a steric polymeric framework via the helical chains. As expected, the Flack parameter of 1 is nearly zero [being 0.01(2)], clearly indicating that the crystal of 1 is a single enantiomer and is also confirmed by the solid-state CD spectrum. Usually, the tetrahedrally coordinated geometry of metal center associated with the linear ligands will result in a diamondoidrelated network; the same theme is found here. Taking tetrahedrally coordinated zinc centers as 4-linking nodes, tma and ddm as 2-connected spacers, the 3D framework topology of 1 is a substantively typical diamondoid network (Figure 3), which is also known for the prototypical NLOactive material KDP-type structure.1e,27 The network can be presented as a Sch€ afli symbol 66 and as a long vertex symbol 62 3 62 3 62 3 62 3 62 3 62 by TOPOS analysis.28 Interestingly, unlike most chiral helical polymeric frameworks that are usually observed on those polymeric solids containing the unsymmertrical or chiral bridging molecules,1e,15c,15e-15g,16e,f,18 the present compound is constructed from zinc centers with tma and ddm that complete symmertrical organic ligands. In most cases, such nonchiral

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components will result in the formation of nonchiral or racemic materials. What is the reason that this enantiopure compound is obtained? The real mechanism of the reaction is not clear at this stage, but nonetheless a few speculations can be made. We gather that the steric selectivity of tma molecule associated with the flexility of ddm ligand may be mainly responsible for this interesting phenomenon. Note that the tma ligand has an uncoordinated carboxylate that is obviously responsible for the assembly of the present chiral helical polymeric framework. At first glance, this uncoordinated carboxylate seems to be a trivial or redundant group for the present compound. However, replacement of the tma molecule with some ligand molecules without this redundant carboxylate group, such as isophthalate, 5-aminoisophthalate and 3,5-pyrdinedicarboxylate or 2,4-pyrdinedicarboxylate, in the same reaction cannot yield the mimicked chiral helical polymeric framework analogous to compound 1. Further inspection shows that the uncoordinated carboxylate groups between neighboring helical Zn-tma chains are actually contacting each other by strong H-bonding (O 3 3 3 O distances range from 2.74 to 3.41 A˚, Figure 2b), resulting in the bridging tma molecule adopting two twisted unidentate carboxylate groups with Δ-configuration to coordinate the zinc centers, and therefore inducing the packing of the 3D chiral helical polymeric phase of 1. Obviously, these Hbonded interactions are also available for increasing the stability of whole crystal structure of 1. On the other hand, another important factor for the chirality may arise because the ddm ligand has the flexible -CH2- group that allows the whole ddm molecule to fit with the Δ-configurated tma molecules and therefore to spur the formation of this enantiopure compound to be accessible, judging by the observation of conformation of ddm molecule being C1 symmetry in the crystal structure. Electronic Structure and Optical Properties. An intense fluorescent emission spectrum of 1 in the solid state at ambient temperature is observed in the visible range at 420 nm upon excitation at 326 nm, which can be assigned to the ligand-to-metal charge transfer (LMCT) bands (Figure 4). The optical diffuse reflectance spectrum (Figure 5) reveals that 1 has an optical band gap of about 1.8 eV that suggests the title compound is a semiconductor. However, these do not reflect well the 3D chiral helical structural nature, and the effect of this acentric structure clearly can not be understood from above observed properties without the help of the theoretical calculations. The electronic band structure and optical property were calculated for the title compound. The result of scalar totalenergy code CASTEP calculation gives us some insight into the relation between structure and properties. The band structure along high symmetry points of the first Brillouin zone and DOS (densities-of-states) are plotted in Figure 6. (Separate band structures showing only in a window of -5 to 5 eV for clarity is given in Supporting Information, Figure S5.) The calculation indicates an indirect band gap semiconducting behavior for the compound, judging from the fact that the top of the valence bands is located at the S point, the bottom of the conduction bands is located at the G point, the indirect band gap is 2.76 eV, and the direct band gap at G point is 2.78 eV (Table 3). This calculated gap is a little larger than the experimental value mentioned above, which may arise from the limitation of the DFT method that sometimes overestimates the band gap in semiconductors and insulators.29 The conduction band region at about 2.76 to 4.2 eV

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Figure 2. (a) A [010] view showing a 1D “right-hand-helical Zn-tma chain” with a 17.6 A˚ of helical pitch that wrapped around imaginary poles, and (b) a view of a 3D noninterpenetrating framework in 1 fabricated by the interconnected helices through bridging ddm spacers and hydrogen bonding interactions; the hydrogen atoms are omitted for clarity.

contains a relatively small number of states that originate from the contribution of mixing effects of substantial C 2p orbitals with a small amount of O 2p and Zn 4s orbitals. The valence bands can be roughly sorted out into four regions, where the bands lying near the Fermi energy to about -2.0 eV mainly originate from the contribution of the O 2p and C 2p orbitals with a small amount of N 2p orbitals, and the states’ contribution to the bands ranging from -2.0 to -10.95 eV are dominated by the C 2p, O 2p, and Zn 3d orbitals with a small amount of mixing of the N 2p, C 2s, and O2s orbitals; the bands domain at about -10.95 to -16.76 eV mainly come from the states’ contribution of the H 1s and C 2s orbitals with a small amount of mixing of the C 2p and O 2p orbitals, and the bands boundary near -17.16 to -23.49 eV substantially result from the contribution of the O 2s and N 2s orbitals with a small amount of H 1s, C 2s2p, and O 2p orbitals. These band states suggest that the optical absorptions for the title compound should arise from the charge transitions of the O 2p into C 2p orbitals. The optical property calculations give us more insight into understanding this acentric structural effect. Figure 7

presents the calculated imaginary and real parts of the dielectric function for the title compound. The highest peak in the imaginary spectrum is observed at the position near 4.71 eV, 4.73 eV, and 4.69 eV in x, y, and z polarization directions, respectively, indicating the dielectric function is anisotropy, and thus the average value of the highest peak is positioned at 4.71 eV, as resulting substantially from the charge transitions of the O 2p into C 2p states based upon the DOS analysis above. This seems to be slightly overestimated in comparison with the experimental value around 3.0 eV. However, considering that the discrepancy may be due to the difference between the single crystal model and polycrystalline sample,29a,30 the calculation value above is reasonable. Such dielectric function will result in the anisotropic refractive index because the correlations between both are linked by the formula of n2(ω) = ε(ω), where n, ω, and ε refer to refractive index, frequency, and dielectric constant, respectively.30 Figure 8 shows the calculated dispersion of linear refractive index of 1. It can be observed that the refractive indices of 1 in three polarization directions are nz > ny > nx. Either dielectric constants

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Figure 5. Optical diffuse reflectance spectra for 1.

Figure 6. The CASTEP electronic structure calculation results for 1. The lines on the left refer to total DOS (black) and partial DOS of elements (as labeled as to Zn, O, N, C and H) s (blue), p (red), and d (green) orbitals; the dashed lines denote the Fermi level that is set at 0 eV. Figure 3. Topological view showing a diamondoid network (top) based on the 3D framework (bottom) of 1.

Figure 4. Solid-state fluorescent emission (gray) and excitation (red) spectra of 1 at room temperature.

or refractive indices are important optical parameters that connect the optical response properties for the compound. The calculated average dielectric constants of static

Table 3. The State Energy [eV] of the Top of the Valence Band (T-VB) and the Bottom of the Conduction Band (B-CB) at Some k Points for 1 k point

T-VB

B-CB

G(0.000 0.000 0.000) Z(0.000 0.000 0.500) T(-0.500 0.000 0.500) Y(-0.500 0.000 0.000) S(-0.500 0.500 0.000) X(0.000 0.500 0.000) U(0.000 0.500 0.500) R(-0.500 0.500 0.500)

-0.021381 -0.055127 -0.055774 -0.000276 0 -0.045283 -0.055792 -0.055663

2.761778 2.765798 2.905226 2.904935 2.906355 2.765912 2.765950 2.907341

Figure 7. Calculated imaginary and real dispersions of the dielectric function for 1 in three different polarization directions.

case ε(0) are 2.38, and the calculated refractive indices in three polarization directions at the wavelength of 1064 nm

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Figure 8. Calculated dispersions of linear refractive index of 1.

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are nx=1.55, ny=1.56, and nz=1.60, respectively. The secondorder susceptibilities calculation31 suggest that the title compound has a second harmonic generation (SHG) response approximately 4 times that of KDP.

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Conclusion In summary, the title compound represents an interesting and remarkable 3D chiral helical polymeric framework. Some of this remarkability must certainly arise from the fabrication based on complete symmetrical organic ligands. Supramolecular hydrogen bonding interaction clearly plays an important role in controlling the packing or assembly for this 3D chiral helical polymeric framework. The experimental observation and the theoretical calculation show that the compound has a band gap semiconducing character, and the optical property calculations reveal that this 3D chiral helical single enantiomorphic framework is a potential NLO-active material having SHG efficiency about 4 times of KDP. We are of course continuing to expect other more novel examples of NLO-active solids in this coordination polymeric area. Acknowledgment. This research was supported by the Natural Science Foundation of China (No. 50971063), the Natural Science Foundation of Fujian Province of China (No. 2003F006), and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry of China. The authors are grateful to Prof. Y.-P. Ruan for the assistance with the solid-state CD data collection and to Dr. Y.-L. Chen for helpful discussions on optical diffuse reflectance spectra. Supporting Information Available: X-ray crystallographic file in CIF format (that has also been deposited as CCDC-699796 in the Cambridge Crystallographic Data Centre), and additional crystallographic information, TGA trace, comparison of observed and calculated XRD powder patterns, IR spectrum, solid-state CD spectrum, and separate DOS projections for the orbitals by elements and band dispersions, and the calculated dispersions of refractive indices for 1. These are available free of charge via the Internet at http://pubs.acs.org.

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