Structural Diversity and Vibrational Spectra of Nine Cu(I)-Cyanide

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Structural Diversity and Vibrational Spectra of Nine Cu(I)-Cyanide MetalOrganic Frameworks with in situ Generated N-Heterocyclic Ligands Min Shao, Ming-Xing Li, Zhao-Xi Wang, Xiang He, and Heng-Hua Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00967 • Publication Date (Web): 30 Oct 2017 Downloaded from http://pubs.acs.org on November 6, 2017

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Crystal Growth & Design

Structural Diversity and Vibrational Spectra of Nine Cu(I)-Cyanide Metal-Organic Frameworks with in situ Generated N-Heterocyclic Ligands Min Shao,†,‡ Ming-Xing Li,*,† Zhao-Xi Wang,† Xiang He,† and Heng-Hua Zhang‡ †

Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China.

‡

Laboratory for Microstructures, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China. RECEIVED DATE

Abstract: Nine Cu(I)-cyanide metal-organic frameworks (MOFs), namely [Cu4(CN)2(4-bpt)2]n (1), {[Cu3(CN)2(4-bpt)]·H2O}n (2), [Cu2(CN)(3-bpt)]n (3), [Cu2(CN)2(3-Hptz)]n (4), [Cu3(CN)2(3-ptz)]n (5), [Cu7(CN)7(3-tpt)2]n (6), {[Cu9(CN)9(btb)2]·btb}n (7), [Cu2(CN)2(4-azpy)]n (8), and [Cu3(CN)3(bpp)]n (9) (4/3-Hbpt = 3,5-bis(4/3-pyridyl)-1,2,4-triazole; 3-Hptz = 3-pyridyl-tetrazole; 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine; btb = 1, 4-bis(1,2,4-triazol-4-yl)benzene; 4-azpy = 4,4'-azobispyridine; bpp = 1,3-bis(4-pyridyl)propane), were synthesized under hydrothermal conditions and structurally characterized. The 4-bpt, 3-bpt and 3-Hptz ligands in 1–4 were in situ generated by cycloaddition reactions. Their structural features vary from 2D (3), 3D (4, 5, 6), 3D 2-fold interpenetration (1, 2, 8), to 3D 3-fold interpenetration (7, 9). Complex 1 is an intriguing 3D MOF with nanosized rectangular channel. Complex 3 exhibits a chiral 2D double-layered network prepared by achiral component. Complex 6 is a 3D MOF constructing from six µ2-cyanides, a µ3-cyanide and a µ3-tpt ligand. Complex 7 shows an interesting 3D MOF with (3.4)-connected 5-nodal net, containing btb guest molecule in the rectangular channel. Complex 8 is a 3D MOF assembled by 2D [Cu2(CN)2]n network pillared by 4-azpy spacer. Complex 9 is a 3D MOF with ths topology. Their structural diversity originates from the variation of Cu(I) coordination numbers and three types of cyanide-bridging modes, tuned via various bidentate (4-azpy, bpp), tridentate (3-Hptz, 3-tpt) and tetradentate (4-bpt, 3-bpt, 3-ptz, btb) N-heterocyclic ligands. Infrared spectra and cyanide coordination modes are discussed in detailed. The characteristic ν(C≡N) stretching frequencies in µ2-CN complexes show linear correlation with the Cu−CN bond distances. A decrease of about 6.7 cm−1 in ν(C≡N) corresponds to a 0.01 Å elongation of Cu−CN bond. These Cu(I) complexes exhibit good thermally stable, and emit strong luminescence in 386–593 nm. Keywords: Copper(I) cyanide, Metal-organic framework, Crystal structure, Coordination mode, Vibrational spectroscopy, Luminescence. INTRODUCTION Metal-organic framework (MOF) and coordination polymer have attracted great interest owing to their intriguing structural motifs and potential applications as functional materials.1–5 Much effort has been focused on the rational design and controlled synthesis of MOFs using rigid and flexible multidentate N-heterocyclic ligands such as triazole, tetrazole and pyridyl derivates.6–11 Most of N-heterocyclic ligands exhibit varied coordination modes which make them very appealing for design of MOFs with interesting structures and functional properties. However, it is still difficult to predict their exact structures, since many factors influence the resulting complexes.12–14 Interestingly, some N-heterocyclic ligands can be in situ generated in

hydrothermal reactions. For example, Zhang and Chen have carried out a series of reactions using M(II) ions, nitriles, and ammonia to prepare 3,5-disubstituted 1,2,4-triazole complexes.15–17 Xiong, et al. have developed the DemkoSharpless [2+3] cycloaddition reaction of nitrile and azide to produce tetrazole complexes by in situ hydrothermal reaction.18–21 Beginning from Prussian blue, cyanide compounds have a long history in inorganic chemistry. Over the past two decades, transition metal cyanides were studied extensively due to their great importance in magnetism and electron transfer.22–25 Meanwhile, copper(I) cyanide system is an active research area with special attention paid to their network structure and luminescence.26–30 Cu(I)-cyanide

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system is attractive from the viewpoint of crystal engineering. Cyanide group, as a small anion with little steric hindrance, is a perfect candidate as linear connector.31,32 It is well-known that CuCN has two linear polymorphs. One is a 1D wave-like chain at room temperature. The other one is a linear chain at high temperature (over 565 °C).33,34 In both cases, copper(I) features a low 2-coordinated center. Cu(I) ion is in favor of trigonal or tetrahedral coordination in the presence of cyanide and N-heterocyclic ligands, which gives the possibility of promoting the formation of high-dimensional Cu(I)-cyanide framework. As a result, CuCN chain has a strong tendency to acquire neutral N-heterocyclic ligand to extend the 2-coordinated Cu(I) to 3- or 4-coordinated center. The synthetic strategies are either combining N-heterocycle to 1D CuCN chain, or using Cu(II) salt as precursor and K3[Fe(CN)6] as cyanide source to afford Cu(I)-cyanide complex under hydrothermal condition.26,35,36 Previously, a number of Cu(I)-cyanide networks incorporating N-heterocycles were documented.37–40 In the course of our investigation to Cu(I)-cyanide complexes,41–45 nine novel Cu(I)-cyanide MOFs were assembled from seven N-heterocyclic ligands (Scheme 1). Their structural diversity and infrared spectra are studied in detailed. Scheme 1. Schematic Drawing of N-Heterocyclic Ligands N

N

N

N N

N

N N

N

4-bpt

3-bpt H N N

N

N N

N N

3-Hptz N N

N

N

N

N

N

btb N

N

N

N

3-tpt

N

N N

4-azpy

N N

bpp

N

EXPERIMENTAL SECTION Materials and Methods. Btb and 3-tpt ligands were prepared according to literature methods.42,46,47 Other chemicals were of reagent grade and used as received without further purification. Elemental analyses (C, H, and N) were performed on a Vario EL III elemental analyzer. Infrared spectra were recorded with a Nicolet A370 FT-IR spectrometer using KBr pellets in 400–4000 cm–1. Thermogravimetric analyses (TGA) were carried out on a Netzsch STA 449C thermal analyzer in 20–800 °C at a heating rate of 10 °C min–1 in air. Luminescent spectra of solid samples were recorded on a Shimadzu RF-5301 spectrophotometer. Synthesis of Complexes 1–9. [Cu4(CN)2(4-bpt)2] n (1). A mixture of Cu(NO3)2.3H2O

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(2.0 mmol), 4-cyanopyridine (10.0 mmol), 3 mL aqueous NH3 (25%), K3[Fe(CN)6] (0.5 mmol), and 5 mL THF was sealed in a 15 mL Teflon-lined reactor and heated at 100 °C for 72 h. Light yellow rod crystals were obtained with 20% yield based on Cu. Anal. Calcd for C26H16Cu4N12: C, 41.60; H, 2.15; N, 22.39. Found: C, 41.16; H, 2.21; N, 22.38. IR: 2119m, 2096m, 1609s, 1421m, 1012m, 836m, 717m cm–1. {[Cu3(CN)2(4-bpt)]·H2O}n (2). A mixture of Cu2(OH)2CO3 (1.0 mmol), 4-cyanopyridine (10.0 mmol), 3 mL aqueous NH3 (25%), K3[Fe(CN)6] (0.5 mmol), and 5 mL H2O was sealed in a 15 mL reactor and heated at 160 °C for 72 h. Several light yellow rod crystals were obtained. Anal. Calcd for C14H10Cu3N7O: C, 34.82; H, 2.09; N, 20.29. Found: C, 35.50; H, 1.83; N, 21.38. IR: 2136m, 2121m, 1611s, 1426m, 1218w, 1011m, 832m, 738m cm–1. [Cu2(CN)(3-bpt)] n (3). A mixture of CuCN (0.3 mmol), 4-amine-3,5-bis(4-pyridyl)-1,2,4-triazole (3-abpt, 0.3 mmol), K3[Fe(CN)6] (0.3 mmol), and 8 mL H2O was sealed in a 15 mL reactor and heated at 180 °C for 72 h. Light yellow rod crystals were obtained with 15% yield. Anal. Calcd for C13H8Cu2N6: C, 41.60; H, 2.15; N, 22.39. Found: C, 42.36; H, 2.14; N, 22.88. IR: 3064w, 2116s, 1605m, 1574m, 1419s, 1181m, 1017m, 815m, 746m, 696s cm–1. [Cu2(CN)2(3-Hptz)] n (4). A mixture of CuCl2.2H2O (1.0 mmol), 3-cyanopyridine (2.0 mmol), NaN3 (3.0 mmol), K3[Fe(CN)6] (0.5 mmol), and 5 mL H2O was sealed in a 15 mL reactor and heated at 110 °C for 72 h. Colorless block crystals were obtained with 45% yield. Anal. Calcd for C8H5Cu2N7: C, 29.45; H, 1.55; N, 30.05. Found: C, 29.46; H, 1.64; N, 29.78. IR: 3165m, 3129m, 3082m, 2121s, 2104s, 1596m, 1553s, 1450m, 1245m, 801s, 744m, 672s cm–1. (Warning: only a small amount of NaN3 can be handled with care) [Cu3(CN)2(3-ptz)] n (5). A mixture of CuCN (0.2 mmol), 3-Hptz (0.2 mmol), K3[Fe(CN)6] (0.1 mmol), and 10 mL H2O was sealed in a 15 mL reactor and heated at 160 ºC for 72 h. Red cubic crystals were obtained with 31% yield. Anal. Calcd for C8H4Cu3N7: C, 24.71; H, 1.04; N, 25.22. Found: C, 25.14; H, 1.01; N, 24.89. IR: 3073w, 3048w, 2103s, 1606m, 1579w, 1458m, 1425s, 1170m, 1041m, 823s, 750m, 697s cm–1. [Cu7(CN)7(3-tpt)2] n (6). A mixture of CuCl2.2H2O (0.2 mmol), 3-tpt (0.1 mmol), K3[Fe(CN)6] (0.2 mmol), and 8 mL H2O was sealed in a 15 mL reactor and heated at 180 °C for 72 h. Light yellow rod crystals were obtained with 25% yield. Anal. Calcd for C43H24Cu7N19: C, 41.26; H, 1.93; N, 21.27. Found: C, 41.37; H, 1.90; N, 21.00. IR: 3061w, 2119s, 2071w, 1600s, 1522s, 1423m, 1359s, 1195m, 1030m, 802s, 698s cm–1. {[Cu9(CN)9(btb)2]·btb}n (7). A mixture of CuCN (0.3 mmol), btb (0.1 mmol), K3Fe(CN)6 (0.2 mmol), 4 mL ethanol, and 4 mL H2O was sealed in a 15 mL reactor and heated at 160 °C for 72 h. Yellow block crystals were


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obtained with 5% yield. Anal. Calcd for C39H24Cu9N27: C, 32.47; H, 1.67; N, 26.22. Found: C, 30.15; H, 1.82; N, 24.00. IR: 3120m, 2161w, 2123s, 1635m, 1541s, 1240m, 1102m, 833s, 641m cm–1. [Cu2(CN)2(4-azpy)] n (8). A mixture of CuCN (0.3 mmol), 4-azpy (0.2 mmol), K3[Fe(CN)6] (0.1 mmol), and 10 mL H2O was sealed in a 15 mL reactor and heated at 160 °C for 72 h. Dark red cubic crystals were obtained with 43% yield. Anal. Calcd for C12H8Cu2N6: C, 39.67; H, 2.22; N, 23.12. Found C, 39.46; H, 2.27; N, 23.40. IR: 3292w, 3046w, 2128s, 2090s, 1607s, 1522m, 1480m, 1413m, 1211m, 1009s, 823s cm–1. [Cu3(CN)3(bpp)] n (9). A mixture of CuCN (0.3 mmol), bpp (0.2 mmol), K3[Fe(CN)6] (0.1 mmol), and 10 mL H2O was sealed in a 15 mL reactor and heated at 160 °C for 72 h. Yellow block crystals were obtained with 54% yield. Anal. Calcd for C16H14Cu3N5: C, 41.16; H, 3.02; N, 15.00. Found: C, 41.08; H, 3.15; N, 15.27. IR: 3079w, 2934m, 2160w, 2124s, 1610s, 1555m, 1423s, 1220m, 1068m, 1018m, 808s cm–1. X-ray Crystallography. The diffraction data of single crystals 1–9 were collected on a Bruker Smart Apex-II CCD diffractometer with graphite monochromatic Mo Kα radiation (λ = 0.71073 Å). The structures were solved by the direct methods and refined on F2 by full-matrix least-square techniques using SHELXTL program.48 Non-hydrogen atoms were anisotropically refined. Hydrogen atoms were placed geometrically and refined using the riding model. The C/N atoms of partial µ2-cyanides in 1, 2, 8 and 9 were undistinguishable, so that each C/N position was set to have the occupancy of 0.5C and 0.5N. Crystallographic data and structural refinements are summarized in Table 1. Selected bond distances and angles are listed in Table S1 (Supporting Information). RESULTS AND DISCUSSION Synthesis. Complexes 1–9 were successfully prepared by hydrothermal reactions. These Cu(I) complexes are quite stable in air. Complexes 3, 5, 7, 8 and 9 were prepared by CuCN and corresponding N-heterocycles in the presence of K3[Fe(CN)6]. Herein, K3[Fe(CN)6] as a supplementary cyanide source can slowly release cyanide upon heat treatment.26,49 Trying to prepare these complexes without K3[Fe(CN)6] failed. Cu(II) salts were used in the preparation of 1, 2, 4 and 6. Cu(II) ion can be reduced to Cu(I) under hydrothermal condition in the presence of N-heterocycle.50,51 Hydrothermal reactions of 4-cyanopyridine, NH3 and K3[Fe(CN)6] with Cu(NO3)2 or Cu2(OH)2CO3 afforded two different complexes, [Cu4(CN)2(4-bpt)2]n (1) and [Cu3(CN)2(4-bpt)]n (2). Obviously, 4-bpt ligand was in situ generated. A mixture of CuCN, 3-abpt and K3[Fe(CN)6]

was heated at 180 °C to afford a 2D network [Cu2(CN)(3-bpt)]n (3). In this procedure, 3-abpt released amino group and converted to 3-bpt. Similar 3-abpt conversion was also observed in previous study.52 By contrast, we prepared a 2D [Cu3(CN)3(4-abpt)2]n network from a mixture of CuCN, 4-abpt and K3[Fe(CN)6], without 4-abpt conversion.53 Yang, et al. prepared a different 3D [Cu2(CN)(bpt)]n MOF by a solvothermal reaction of Cu(Ac)2 and bpt in acetonitrile solvent.54 Recently, our study indicated that cyanide can be in situ generated by the cleavage of acetonitrile.45 [Cu2(CN)2(3-Hptz)]n (4) was prepared by the reaction of CuCl2, 3-cyanopyridine, NaN3 and K3Fe(CN)6. 3-Hptz was in situ generated under hydrothermal condition. This tetrazole-formed reaction involved in the Demko-Sharpless [2+3] cycloaddition by cyano group and azide.55 Trying to prepare 4 directly using 3-Hptz ligand, however, we harvested a new 3D MOF [Cu3(CN)2(3-ptz)]n (5). [Cu7(CN)7(3-tpt)2]n (6) was prepared by the reaction of CuCl2 with 3-tpt and K3[Fe(CN)6]. Obviously, cyanide was originated from K3[Fe(CN)6]. Previously, we reported a beautiful 3D honeycomb MOF [Cu3(CN)3(4-tpt)]n, prepared by the reaction of CuCN with 4-tpt and K3[Fe(CN)6].42 CuCN reacted with btb and K3Fe(CN)6 to afford an interesting 3D MOF {[Cu9(CN)9(btb)2]·btb}n (7), which contains a free btb guest molecule in rectangular channel. The reaction of CuCN with 4-azpy and K3[Fe(CN)6] produced a dark-red 3D MOF [Cu2(CN)2(4-azpy)]n (8), in which the dark-red color originates from the azo-group of 4-azpy. Finally, a 3D MOF [Cu3(CN)3(bpp)]n (9) was obtained by the reaction of CuCN with a flexible bpp ligand and K3[Fe(CN)6]. Crystal Structural Description. [Cu4(CN)2(4-bpt)2]n (1). Complex 1 is a 3D MOF. As depicted in Figure 1a, the asymmetric unit displays Cv symmetry and contains two independent Cu(I) ions, two halves of cyanide, and a 4-bpt ligand. Both Cu(I) centers adopt trigonal geometry. Cu1 combines with two triazole nitrogens and a cyanide. Cu1 and Cu1A are bridged by two triazole groups to form a Cu2N4 six-membered ring. Cu2 combines with two pyridyl groups and a cyanide. Both Cu2–Npy bond distances are 1.986(2) Å. Complex 1 has two distinct µ2-cyanides. One cyanide links Cu1 and Cu1B to form a Cu1–CN–Cu1B dimer. The other cyanide links Cu2 and Cu2B to form a Cu2–CN–Cu2B dimer. The 4-bpt as an exo-tetradentate ligand coordinates to four Cu(I) ions via two triazole nitrogens and two pyridyl groups. The µ2-cyanides and µ4-bpt connect Cu1 and Cu2 to form a beautiful 3D MOF. Viewed along a-axis (Figure 1b), the 3D MOF exhibits hexagonal channel. Each hexagon is constructed by two



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angular 4-bpt ligands and two Cu2–CN–Cu2B units. Such hexagons are further connected by Cu1–CN–Cu1B units to form the 3D framework. As shown in Figure 1c, complex 1 is an intriguing 3D MOF with nanosized rectangular channel. The approximate dimensions of the channel are 1.70 × 0.83 nm2. Each rectangle is constructed by two Cu1–CN–Cu1B units as short edges, and two building blocks (each formed by one Cu2–CN–Cu2B unit linking two 4-bpt terminals) as long edges (also see Figure S1a, Supporting Information). It is noteworthy that complex 1 is a neutral 3D MOF possessing completely empty rectangular channel without any solvent molecule. Further research found that two identical 3D frameworks interpenetrate to each other and generate a smaller 1.4 × 0.5 nm2 channel (Figure S1b). The void volume calculated by PLATON is 11.1%.56

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(Figure 2a). Cu1 and Cu3 both adopt a trigonal geometry. Cu1 is coordinated by triazole N2, pyridyl N4 and cyanide N5. Cu3 combines with a pyridyl group and two cyanides. Cu2 is linearly two-coordinated by triazole N1 and cyanide N6 with a N1–Cu2–N6 bond angle of 170.0(2)º. Similar to 1, 4-bpt in 2 is a tetradentate ligand and combines with four Cu(I) ions via two triazole nitrogens and two pyridyl groups. Two cyanides act as µ2-CN bridges. As a striking structural feature, the µ2-cyanides and triazole groups link Cu1, Cu2 and Cu3 to form a left-handed 21 helical chain with a pitch of 8.047(1) Å (Figure 2b). By the combination of Cu3–Npy bond, these helical chains are parallel arranged and further connected by pyridyl groups to form a 3D MOF. The rhombic channel is generated by the 21 helical CuCN chain (Figure 2c). Complex 2 is two-fold interpenetrated and possesses a 0.8 × 0.7 nm2 channel (Figure S2).

(a)

(b)

(a)

(b)

(c)

(c)

Figure 1. (a) Coordination environment of 1. (b) 3D MOF showing hexagonal channel viewed along a-axis. (c) 3D MOF with rectangular channel. {[Cu3(CN)2(4-bpt)]·H2O}n (2). Complex 2 is a 3D MOF. The asymmetric unit consists of three independent Cu(I) ions, two cyanides, a 4-bpt ligand, and a lattice water

Figure 2. (a) Coordination environment of 2. (b) Lefthanded 21 helical chain. (c) 3D MOF with rhombic channel. [Cu2(CN)(3-bpt)]n (3). Complex 3 is a chiral 2D network, which crystallizes in orthorhombic chiral P212121 space group with a Flack factor of 0.015(18). The asymmetric unit is composed of two Cu(I) ions, a cyanide, and a 3-bpt ligand (Figure 3a). Cu1 and Cu2 both adopt a trigonal geometry, coordinated by a triazole nitrogen, a pyridyl nitrogen and a cyanide. The µ2-CN links Cu1 and Cu2A. The 3-bpt as a tetradentate ligand binds to four Cu(I) ions via two triazole nitrogens and two 3-pyridyl groups. The 3-bpt links Cu1 and Cu2 to form a right-handed 21 Cu-bpt helical chain with a pitch of 7.769(1) Å (Figure 3b). The Cu-bpt helical chains are further connected by µ2-cyanides to form a 2D double-layered network (Figure


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3c). The chirality of 3 originates from the Cu-bpt 21 helical chain.53

(b)

(a)

(b)

(c)

Figure 3. (a) Coordination environment of 3. (b) Cu-bpt 21 helical chain. (c) 2D double-layered network viewed along c- and a-axes. [Cu2(CN)2(3-Hptz)]n (4). Complex 4 is a 3D MOF constructing from two independent Cu(I) ions, a µ2-cyanide, a µ3-cyanide, and a µ3-Hptz ligand (Figure 4a). Cu1 and Cu2 both adopt a distorted tetrahedral geometry. Cu1 is coordinated by three cyanides and tetrazole N2. Cu2 is bound to two cyanides and two tetrazole nitrogens. 3-Hptz is a neutral tridentate ligand, which binds to three Cu(I) ions via three tetrazole N-donors. The pyridyl group is free. Two tetrazole groups connect Cu2 and Cu2A to form a six-membered ring. Two cyanides show µ2-CN and (µ3-CN)2Cu2 coordination modes (Scheme 2). Cu1 and Cu1A are linked by two µ3-cyanides to form a Cu2 dimer. The Cu1···Cu1A separation is 2.585(1) Å, less than the sum of van der Waals radii (2.8 Å), indicating a metal interaction between Cu1 and Cu1A.57 Two distinct cyanides link Cu1 and Cu2 to form a 1D Cu-cyanide double chain, which is further connected by µ3-Hptz to generate a 3D MOF (Figure 4b).

Figure 4. (a) Coordination environment of 4. (b) 1D Cu-cyanide double chain (up) and 3D framework. [Cu3(CN)2(3-ptz)]n (5). Complex 5 is a 3D MOF. The asymmetric unit contains three Cu(I) ions, two µ2-cyanides, and a µ4-3-ptz ligand (Figure 5a). Cu1 and Cu2 both adopt a trigonal geometry, coordinated by a tetrazole nitrogen and two cyanides. Cu3 is linear two-coordinated by pyridyl N5 and tetrazole N3A. Unlike the neutral tridentate 3-Hptz ligand in 4, the tetradentate 3-ptz anionic ligand in 5 coordinates to four Cu(I) ions via three tetrazole nitrogens and a pyridyl nitrogen. The 3-ptz links Cu1, Cu2 and Cu3 to form a 1D [Cu3(3-ptz)]n ribbon, which is further connected by µ2-CN cyanides to generate a 3D MOF (Figure 5b). Previously, Zhai et al. reported a 3D framework [Cu3(CN)2(4-ptz)]n, constructed from a pentadentate 4-ptz, a µ3-cyanide, and two Cu(I) ions.58

(a)

(b)

(a) Figure 5. (a) Coordination environment of 5. (b) 1D [Cu3(3-ptz)]n ribbon (up) and 3D framework. [Cu7(CN)7(3-tpt)2]n (6). Complex 6 is a 3D MOF. The asymmetric unit contains seven independent Cu(I) ions,



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seven cyanides and two 3-tpt ligands (Figure 6a). Two 3-tpt ligands are tridentate, each binds to three Cu(I) ions via three pyridyl groups. Among seven cyanides, six of them are µ2-CN, while the seventh cyanide adopts a µ3-CN mode to combine Cu2, Cu4 and Cu6. Seven Cu(I) ions all adopt trigonal geometry, six of them are coordinated by a pyridyl group and two µ2-cyanides. Cu6 is coordinated by a µ3-cyanide and two µ2-cyanides without pyridyl group. This is consistent with the fact that the asymmetric unit containing seven Cu(I) ions and six pyridyl N-donors from two 3-tpt ligands. Cu4 and Cu6 are linked by the µ3-cyanide with a Cu4···Cu6 separation of 2.503 Å, which is less than the sum of van der Waals radii and indicates a metal interaction between Cu4 and Cu6. Seven cyanides link seven Cu(I) ions to form a 2D Cu-cyanide network that contains [Cu14(CN)14] and [Cu16(CN)16] macrocycles in a 1:1 ratio (Figure 6b). The 14- and 16-membered metal-containing macrocycles are combined together by µ3-CN connector. The exo-tridentate 3-tpt ligand further connects the 2D Cu(I)-cyanide network to afford a 3D MOF (Figure 6c).

(a)

which contains free btb guest molecule in pore. The asymmetric unit consists of 4.5 independent Cu(I) ions, 4.5 µ2-cyanides, a µ4-btb ligand, and a half btb guest molecule (Figure 7a). Cu1 (0.5 occupancy) is located at an inversion center, linearly two-coordinated by two cyanides. Cu2 and Cu3 are three-coordinated by three cyanides. Cu4 and Cu5 are three-coordinated by a cyanide and two triazole N-donors. All the cyanides as µ2-CN bridges link Cu1, Cu2, Cu3 and Cu4 to form a 1D Cu-cyanide ribbon (Figure S3a). Neutral tetradentate btb ligand connects Cu4/Cu5 and Cu4A/Cu5A via two triazole groups, constructing a 1D [Cu2(btb)]n double chain. Two adjacent [Cu2(btb)]n double chains are parallel arranged and further connected by µ2-CN to afford a 1D [Cu4(CN)(btb)2]n ribbon (Figure S3b). This 1D ribbon is cross-linked nearly perpendicularly with the 1D Cu-cyanide ribbon via the µ2-C4≡N4 connection, resulting in the formation of a regular 3D MOF with nanosized rectangular channel (Figure 7b). The approximate dimensions of the channel are 1.44 × 0.89 nm2. The 3D framework can be simplified as a (3.4)-connected 5-nodal net. The Schäfli notation is {4;122}{4;62}{42;6;82;10}{6;122}{62;10}. Further research found that the 3D framework is three-fold interpenetrated, as depicted in Figure 7c. Interestingly, free btb guest molecule is incorporated into the channel (Figure 7d). This beautiful 3D MOF reveals that btb is a valuable rigid multidentate ligand, although very few effort was devoted to btb complex so far.59–61

(a)

(b)

(b) (c)

Figure 6. (a) Coordination environment of 6. (b) 2D Cu-cyanide network. (c) 3D MOF with the 2D Cu-cyanide network (red). {[Cu9(CN)9(btb)2]·btb}n (7). Complex 7 is a 3D MOF

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(c)


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(d)

Figure 7. (a) Coordination environment of 7. (b) 3D MOF with rectangular channel. (c) Three-fold interpenetration. (d) 3D MOF filled btb guest molecule (red). [Cu2(CN)2(4-azpy)]n (8). Complex 8 is a 3D MOF. The asymmetric unit contains two Cu(I) ions, two cyanides, and a 4-azpy (Figure 8a). Two distinct cyanides exhibit µ2-CN and (µ3-CN)2Cu2 coordination modes. Cu1 locates at a tetrahedral geometry completed by three cyanides and pyridyl N2. Cu1 and Cu1A are linked by two µ3-cyanides to form a Cu2 dimer with a Cu1···Cu1A separation of 2.526 Å, indicating a metal interaction between Cu1 and Cu1A. Cu2 is three-coordinated by two µ2-cyanides and pyridyl N5 to complete a trigonal geometry. Bidentate 4-azpy ligand links Cu1 and Cu2 via two pyridyl terminals. Two pyridyl rings twist 59.1(2)º to each other. Cu1 and Cu2 are linked by µ2-cyanide and µ3-cyanide to afford a 2D wave-like [Cu2(CN)2]n network with rectangular grid (Figure 8b). The approximate dimensions of the rectangle are 1.35 × 0.68 nm2. The 2D Cu(I)-cyanide networks are parallel arranged and further pillared by 4-azpy spacer to generate a 3D porous MOF (Figure 8c). The 3D framework is two-fold interpenetrated, as shown in Figure S4.

Figure 8. (a) Coordination environment of 8. (b) 2D [Cu2(CN)2]n network. (c) 3D MOF assembled by wave-like [Cu2(CN)2]n network pillared by 4-azpy spacer. [Cu3(CN)3(bpp)]n (9). Complex 9 is a 3D MOF. The asymmetric unit contains three Cu(I) ions, three µ2-cyanides, and a bpp ligand (Figure 9a). Cu1 and Cu3 adopt a trigonal geometry, coordinated by two cyanides and a pyridyl group. Cu2 is linearly two-coordinated by two µ2-cyanides with a C1–Cu2–N1 bond angle of 154.6(2)°. Bpp links Cu1 and Cu3 via two pyridyl terminals. The dihedral angle between two pyridyl rings is 32.8(1)°. Cu1 is linked by µ2-cyanide to form a 1D [CuCN]n zigzag chain, while Cu2 and Cu3 are connected by µ2-cyanide to form a 1D wave-like [Cu2(CN)2]n chain (Figure S5a). The [CuCN]n zigzag chain and the [Cu2(CN)2]n wave-like chain are nearly perpendicular to each other, which are further cross-linked via µ2-bpp spacer to form a 3D MOF (Figure 9b). The whole framework can be simplified as a 3-connected ths topology with the Schäfli notation of {103}. The 3D framework is three-fold interpenetrated (Figure S5b). Previously, a 2D wave-like [Cu4(CN)4(bpp)2]n network was reported.62

(a)

(b) (a)

(b)

Figure 9. (a) Coordination environment of 9. (b) 3D MOF.

(c)

Structural Diversity and Cyanide Coordination Modes. Generally, Cu(I) favors linear two-coordinate, trigonal three-coordinate, or tetrahedral four-coordinate geometries. In above nine complexes, various coordination geometries around Cu(I) centers are observed. Cu(I) ions in 1, 3 and 6 all adopt trigonal geometry. Two Cu(I) ions in 4 locate at a tetrahedral geometry. Complexes 2, 5 and 9 possess a linear two-coordinated Cu(I) and two three-coordinated Cu(I) ions. Complex 7 has 0.5 two-coordinated Cu(I) and four trigonal Cu(I) ions. Complex 8 has a trigonal Cu(I) and a tetrahedral Cu(I).



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Cyanide coordination is varied in transition metal complexes. Guo and Mak pointed out that there are nine types of cyanide coordination modes.63 However, the coordination in Cu(I)-cyanide complexes is quite simple. Except few terminal-cyanide Cu(I) complexes, Pike depicted that there are three types of cyanide bridging coordination modes in Cu(I) complexes,37 µ2-CN, µ3-CN and (µ3-CN)2Cu2 dimer with a Cu···Cu interaction (Scheme 2). We ran a CCDC search and found that more than 300 compounds have µ2-CN, and about 30 compounds have (µ3-CN)2Cu2.26,64,65 However, the µ3-CN is rare.66,67 In complexes 1–9, cyanides exhibit µ2-CN, µ3-CN and (µ3-CN)2Cu2 modes, resulting in their different 2D and 3D structural features. In 1, 2, 3, 5, 7 and 9, all the cyanides adopt simple µ2-CN bridging mode. 4 and 8 both possess a µ2-CN and a (µ3-CN)2Cu2. Only a µ3-CN is found in [Cu7(CN)7(3-tpt)2]n (6), in which other six cyanides adopt µ2-CN mode. Scheme 2. Cyanide Coordination Modes in Cu(I) Complexes

terminal

µ2-CN

µ3-CN

(µ3-CN)2Cu2

Seven different N-heterocycles in 1–9 exhibit varied coordination fashions. 1, 2 and 3 have a tetradentate 4/3-bpt. 4 possesses a tridentate 3-Hptz, while 5 has a tetradentate 3-ptz. 6 possesses two tridentate 3-tpt ligands. 7 has a tetradentate btb ligand and a free btb guest molecule. In 8 and 9, 4-azpy and bpp act as bidentate linkers. In the nine Cu(I)-cyanide complexes, most of them are 3D MOFs, except 3 is a 2D double-layered network. Obviously, the structural diversity originates from the variation of Cu(I) coordination geometries and cyanide coordination modes as well as the addition of various N-heterocyclic ligands. It is noteworthy that no coordinated or lattice water was found in these complexes, except 2 has a lattice H2O. This is in accordance with the fact that Cu(I) is a soft-acid and H2O is a hard-base, which further indicates that Cu(I)-cyanide MOFs have hydrophobic feature. Vibrational Spectroscopy of Cyanide Coordination. The infrared spectra of 1–9 are collected in Figure S6. Their cyanide characteristic band, corresponding coordination mode and cyanide number are summarized in Table 2. Generally, cyanide (C≡N) exhibits strong characteristic band in 2050−2200 cm−1 range. In pure

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CuCN, the ν(C≡N) stretching vibration occurs at 2170 cm−1.37 In 1–9, cyanides adopt µ2-CN, µ3-CN and (µ3-CN)2Cu2 coordination modes. Viewing the ν(C≡N) data, the characteristic bands of µ2-CN occur in 2161–2096 cm–1 range. The bands of (µ3-CN)2Cu2 in 4 and 8 occur at 2104 and 2086, respectively. The band of µ3-CN in 6 occurs at 2071 cm–1. Obviously, the frequency of µ3-cyanide is lower than that of µ2-CN. Complexes 1 and 2 both contain two distict µ2-cyanides in 1:1 ratio. Their IR spectra show two µ2-C≡N characteristic peaks in equal intensity. The cyanides in 3 and 5 display single band, indicating that they are bound to Cu(I) in sole µ2-CN mode. In complex 5, two independent µ2-cyanides have similar Cu–CN bond distances. The average (av.) bond distance of 1.916 Å is listed in Table 2. The µ2-cyanides coexist with (µ3-CN)2Cu2 in 4 and 8, and with µ3-CN in 6. Their IR spectra show two cyanide characteristic bands. In spectrum 7, a strong band at 2123 cm–1 is assigned to four µ2-CN bridges with longer Cu–CN bond distances (av. 1.883 Å), while a weak peak at 2161 cm–1 is attributed to 0.5 µ2-CN binding to Cu1 center with a short Cu–CN bond distance (1.829 Å). Similarly, a strong peak at 2124 cm–1 is assigned to two µ2-CN bridges in 9, and a weak peak at 2160 cm–1 is attributed to a µ2-CN with short Cu–CN bond distance (1.832 Å). Table 2. IR Characteristic Bands of Cyanides in 1–9 Cyanide (number) νC≡N (cm–1) 211 2119m µ2-CN (2) 2096m {[Cu3(CN)2(4-bpt)]·H2O}n (2) µ2-CN (2) 2136m 2121m 2116s [Cu2(CN)(3-bpt)]n (3) µ2-CN (1) [Cu2(CN)2(3-Hptz)]n (4) 2121s µ2-CN (1) 2104s (µ3-CN)2Cu2 (1) [Cu3(CN)2(3-ptz)]n (5) 2103s µ2-CN (2) [Cu7(CN)7(3-tpt)2]n (6) 2119s µ2-CN (6) 2071w µ3-CN (1) {[Cu9(CN)9(btb)2]·btb}n (7) µ2-CN (4.5) 2123s 2161w 2128s [Cu2(CN)2(4-azpy)]n (8) µ2-CN (1) 2086s (µ3-CN)2Cu2 (1) [Cu3(CN)3(bpp)]n (9) 2124s µ2-CN (3) 2160w Complex [Cu4(CN)2(4-bpt)2]n (1)

Cu–CN (Å) 1.899 1.915 1.859 1.887 1.890 1.902 1.938, 2.378 1.916 (av.) 1.887 (av.) 1.980, 2.162 1.883 (av.) 1.829 1.891 2.015, 2.241 1.884 (av.) 1.832

Figure 10. Plots of the wavenumber of the ν(C≡N) band


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against the Cu–CN (µ2-CN) bond distance. Interestingly, the ν(C≡N) stretching frequency is sensitive to the strength of Cu–CN bond. In the nine Cu(I)-cyanide complexes, the ν(C≡N) wavenumbers show linear correlation with the Cu−CN bond distances, especially in the case of µ2-CN mode. As depicted in Figure 10, a decrease of about 6.7 cm−1 in ν(C≡N) frequency corresponds to a 0.01 Å elongation of Cu–CN bond. This result can be explained in term of the Cu/CN bonding interaction. Although cyanide is a π-bonding ligand, previous study indicates that the π back-bonding interaction of Cu/CN is quite weak.68,69 The µ2-CN coordination with relatively strong σ donation to Cu(I) results in an increase of ν(C≡N) frequency.37,70,71 Similar phenomenon was also observed in Ag–CN complexes.72 A correlation between ν(C≡N) stretching frequency and Ag−CN bond distance exists in a number of Ag-cyanide complexes, decreasing ν(C≡N) frequency with increasing Ag−CN bond distance.73 The correlation between ν(C≡N) frequency and Cu−CN bond distance indicates that infrared spectroscopy is a valuable tool to sense the structural diversity of Cu(I)-cyanide complexes, especially when their crystal structures are difficult to obtain. Thermogravimetry. Thermal behaviors of 1–9 were investigated in 20–800 °C, except 2 and 7 due to poor yield (Figure S7). Bpt complexes 1 and 3 were thermally stable up to 400 °C, and then rapidly decomposed. Pyridyl-tetrazole complex 4 was stable to 270 °C, and then rapidly decomposed to afford a stable CuO residue at 640 °C (obsd 50.0%, calcd 48.8%). Similarly, 3-ptz complex 5 was stable to 330 ºC, and then explosively decomposed to leave a CuO residue at 530 ºC (obsd 62.7%, calcd 61.3%). This phenomenon is attributed to the unstability of nitrogen-rich tetrazole compounds.74 Therefore, only a small amount of pyridyl-tetrazole complexes 4 and 5 can be handled with care. 3-Tpt complex 6 was stable to 350 °C, and then successively decomposed to 800 °C without stopping. 4-Azpy complex 8 was stable to 260 °C, and then gradually decomposed to afford a CuO residue at 750 °C (obsd 44.8%, calcd 43.8%). Bpp complex 9 was stable to 236 °C, and then released a bpp ligand in 236–403 °C (obsd 41.5%, calcd 42.4%). [Cu(CN)]n intermediate decomposed to 580 °C, left a stable CuO residue (obsd 46.1%, calcd 51.1%). Thermal analysis results indicate that these Cu(I)-cyanide MOFs are quite stable. Especially 1 and 3, both complexes are thermally stable up to 400 ºC. Photoluminescence. It is well known that d10 Cu(I) complexes exhibit various luminescence. Organic ligands and coordination modes

remarkably affect their emission wavelength and mechanism.75,76 Usually, metal-to-ligand charge transfer (MLCT) is the most common assignment to Cu(I)-cyanide complexes,77 where the electron is transferred from Cu(I) to π* orbital of cyanide.78 CuCN has an intense MLCT emission at 392 nm, which can be obviously red-shifted by N-heterocyclic coordination.37 In this work, the luminescent behaviors of 1–9 were investigated, except 2 and 7 due to poor yield (Figure S8). Excited with 316 nm light, complex 1 exhibits an intense emission peak at 386 nm, which is nearly equal to the 380 nm emission of free 4-bpt ligand, indicating a ligand-centered emission. The 3-bpt complex 3 shows a yellow emission peak at 573 nm under excited at 383 nm. Remarkable red-shift emission peak suggests that the most possible emission mechanism is MLCT. By contrast, 1 and 3 have similar molecular composition, both constructed from trigonal Cu(I), tetradentate 4/3-bpt ligands and µ2-cyanides. However, the former is a 3D MOF, while the latter is a 2D chiral network. The structural difference results in their emission energy and mechanism being different. Excited at 391 nm, 4 and 5 are similar orange emitters with emission maxima respectively at 589 and 593 nm, which are assigned to MLCT mechanism. 6 displays a broad violet emission band with maximum at 413 nm (λex = 357 nm), which is comparable with the 380 nm emission peak of free 3-tpt ligand, indicating a ligand-centered emission. 8 emits green luminescence at 414 nm (λex = 350 nm), corresponding to 4-azpy ligand-centered emission. Due to flexibility, free bpp ligand shows a very weak emission at 523 nm. However, bpp complex 9 exhibits an intense blue emission at 470 nm (λex = 390 nm). This emission originates from MLCT mechanism. CONCLUSIONS Nine novel Cu(I)-cyanide MOFs were successfully constructed from seven N-heterocyclic ligands. Three N-heterocycles were in situ generated. Most of them are porous with nanosized channels. The versatile coordination modes and characteristics IR spectra of cyanide are summarized. The characteristic ν(C≡N) stretching frequency in µ2-CN complexes correlates well with the Cu−CN bond distances. A decrease of about 6.7 cm−1 in ν(C≡N) frequency corresponds to a 0.01 Å elongation of Cu−CN bond. These Cu(I)-cyanide complexes exhibit good thermally stable, and emit strong luminescence in 386–593 nm. The results prove CuCN is an ideal linear building block in assembling porous MOFs. Infrared spectroscopy is a valuable tool to sense the structural diversity of Cu(I)-cyanide complexes. ASSOCIATED CONTENT



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Supporting Information. Bond distances and angles, structural figures, IR spectra, TGA curves, and emission spectra. CCDC: 610198 (1), 1038962 (2), 652453 (3), 1038963 (4), 1038964 (5), 683389 (6), 1038965 (7), 1038966 (8), and 1038968 (9). This information is available free of charge via the Internet at http://pubs.acs.org/. AUTHOR INFORMATION Corresponding Author: *(M.-X.L.) E-mail: [email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was financially supported by Natural Science Foundation of Shanghai (17ZR1410600, 16ZR1411400) and National Natural Science Foundation of China (21171115). REFERENCES (1) Zhou, H. C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112, 673. (2) Cook, T. R.; Zheng, Y. R.; Stang, P. J. Chem. Rev. 2013, 113, 734. (3) Perry IV, J. J.; Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400. (4) Lin, Z. J.; Lü, J.; Hong, M. C.; Cao, R. Chem. Soc. Rev. 2014, 43, 5867. (5) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004, 43, 2334. (6) Janiak, C.; Vieth, J. K. New J. Chem. 2010, 34, 2366. (7) Dong, M. M.; He, L. L.; Fan, Y. J.; Zang, S. Q.; Hou, H. W.; Mak, T. C. W. Cryst. Growth Des. 2013, 13, 3353. (8) Ouellette, W.; Liu, H.; O’Connor, C. J.; Zubieta, J. Inorg. Chem. 2009, 48, 4655. (9) Hu, J. S.; Yao, X. Q.; Zhang, M. D.; Qin, L.; Li, Y. Z.; Guo, Z. J.; Zheng, H. G.; Xue, Z. L. Cryst. Growth Des. 2012, 12, 3426. (10) Liu, X. G.; Wang, L. Y.; Zhu, X.; Li, B. L.; Zhang, Y. Cryst. Growth Des. 2009, 9, 3997. (11) Liu, J. J.; He, X.; Shao, M.; Li, M. X. J. Mol. Struct. 2009, 919, 189. (12) Zhan, S. Z.; Li, M.; Zhou, X. P.; Ni, J.; Huang, X. C.; Li, D. Inorg. Chem. 2011, 50, 8879. (13) Lu, Z. Z.; Zhang, R.; Li, Y. Z.; Guo, Z. J.; Zheng, H. G. J. Am. Chem. Soc. 2011, 133, 4172. (14) Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502. (15) Zhang, J. P.; Zheng, S. L.; Huang, X. C.; Chen, X. M. Angew. Chem., Int. Ed. 2004, 43, 206. (16) Zhang, J. P.; Lin, Y. Y.; Huang, X. C.; Chen, X. M. J. Am. Chem. Soc. 2005, 127, 5495. (17) Cheng, L.; Zhang, W. X.; Ye, B. H.; Lin, J. B.; Chen, X. M. Inorg. Chem. 2007, 46, 1135. (18) Xiong, R. G.; Xue, X.; Zhao, H.; You, X. Z.; Abrahams, B. F.; Xue, Z. Angew. Chem., Int. Ed. 2002, 41, 3800.

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2008, 149. (47) Herbst, R. M.; Garrison, J. A. J. Org. Chem. 1953, 18, 872. (48) Sheldrick, G. M. SHELXTL, Version 6.1, Bruker AXS Inc., Madison, WI, USA, 2000. (49) Mao, H.; Zhang, C.; Xu, C.; Zhang, H.; Shen, X.; Wu, B.; Zhu, Y.; Wu, Q.; Wang, H. Inorg. Chim. Acta 2005, 358, 1934. (50) Lu, J. Y.; Babb, A. M. Inorg. Chem. 2002, 41, 1339. (51) Dybtsev, D. N.; Chun, H.; Kim, K. Chem. Commun. 2004, 1594. (52) Zhai, Q. G.; Zhang, C. F.; Li, S. N.; Jiang, Y. C.; Hu, M. C. J. Coord. Chem. 2013, 66, 4004. (53) Chen, N.; Li, M. X.; Yang, P.; He, X.; Shao, M.; Zhu, S. R. Cryst. Growth Des. 2013, 13, 2650. (54) Yang, L; Xin, L.; Tian, J.; Du, P.; Wei, X.; Liao, S.; Zhang, Y.; Lv, R.; Gu, W.; Liu, X. J. Mol. Struct. 2014, 1064, 1. (55) Wang, X. S.; Tang, Y. Z.; Huang, X. F.; Qu, Z. R.; Che, C. M.; Chan P. W. H.; Xiong, R. G. Inorg. Chem. 2005, 44, 5278. (56) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; Utrecht University: Utrecht, The Netherlands, 2002. (57) Che, C. M,; Lai, S. W. Coord. Chem. Rev. 2005, 249, 1296. (58) Zhai, Q. G.; Chen, S. Q.; Li, S. N.; Jiang, Y. C.; Hu, M. C. J. Inorg. Organomet. Polym. 2013, 23, 1195. (59) Wang, N.; Ma, J. G.; Shi, W.; Cheng, P. CrystEngComm 2012, 14, 5634. (60) Bondar, O. A.; Lukashuk, L. V.; Lysenko, A. B.; Krautscheid, H.; Rusanov, E. B.; Chernega, A. N.; Domasevitch, K. V. CrystEngComm 2008, 10, 1216. (61) Peng, Y. F.; Zheng, L. Y.; Han, S. S.; Li, B. L., Li, H. Y. Inorg. Chem. Commun. 2014, 44, 41. (62) Su, Z.; Zhao, Z.; Zhou, B.; Caia, Q.; Zhang, Y. CrystEngComm 2011, 13, 1474. (63) Guo, G. C.; Mak, T. C. W. Angew. Chem., Int. Ed. 1998, 37, 3183. (64) Deng, H,; Qiu, Y.; Daiguebonne, C.; Kerbellec, N.; Guillou, O.; Zeller, M.; Batten, S. R. Inorg. Chem. 2008, 47, 5866. (65) Stocker, F. B.; Staeva, T. P.; Rienstra, C. M.; Britton, D. Inorg. Chem. 1999, 38, 984. (66) Liang, S. W.; Li, M. X.; Shao, M.; Miao, Z. X. Inorg. Chem. Commun. 2006, 9, 1312. (67) Chu, D. Q.; Wang, L. M.; Xu, J. Q. Mendeleev Commun. 2004, 14, 25. (68) Kettle, S. F. A.; Diana, E.; Boccaleri, E.; Stanghellini, P. L. Inorg. Chem. 2007, 46, 2409. (69) Kettle, S. F. A.; Diana, E.; Marchese, E. M. C.; Boccaleri, E.; Croce, G.; Sheng, T.; Stanghellini, P. L. Eur. J. Inorg. Chem. 2010, 3920. (70) Pinakoulaki, E.; Vamvouka, M.; Varotsis, C. J. Phys. Chem. B 2003, 107, 9865. (71) Bowmaker, G. A.; Kennedy, B. J.; Reid, J. C. Inorg. Chem. 1998, 37, 3968. (72) Bowmaker, G. A.; Effendy; Reid, J. C.; Rickard, C. E. F.; Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton Trans. 1998, 2139. (73) Bowmaker, G. A.; Hartl, H.; Urban, V. Inorg. Chem. 2000, 39, 4548. (74) Li, M. X.; Zhang, Y. F.; He, X.; Shi, X. M.; Wang, Y. P.;

Shao, M.; Wang, Z. X. Cryst. Growth Des. 2016, 16, 2912. (75) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112, 1126. (76) Ford, P. C.; Cariati, E.; Bourassa, J. Chem. Rev. 1999, 99, 3625. (77) Colacio, E.; Kivekas, R.; Lloret, F.; Sunberg, M.; SuarezVarela, J.; Bardaji, M.; Laguna, A. Inorg. Chem. 2002, 41, 5141. (78) Liu, X.; Guo, G. C.; Wu, A. Q.; Cai, L. Z.; Huang, J. S.; Inorg. Chem. 2005, 44, 4282.



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 17

Table 1. Crystallographic Data and Structure Refinement for 1–9 complex

1

2

3

4

5

formula

C13H8Cu2N6

C13H8Cu3N8O

C13H8Cu2N6

C8H4Cu2N7

C8H4Cu3N7

fw

375.35

482.89

375.33

325.26

388.80

cryst syst

monoclinic

monoclinic

orthorhombic

triclinic

triclinic

space group

P2/m

P21/n

P212121

Pī

Pī

a (Å)

5.2755(7)

7.8677(3)

7.7690(7)

7.9901(10)

7.8385(8)

b (Å)

15.4282(19)

8.0468(3)

7.8659(7)

8.9892(18)

8.8547(9)

c (Å)

8.2805(10)

25.1679(10)

21.031(2)

9.0317(11)

9.3060(10)

α (deg)

90

90

90

106.226(2)

62.7410(10)

β (deg)

92.496(2)

95.013(2)

90

115.6990(10)

65.4500(10)

γ (deg)

90

90

90

103.579(2)

75.5090(10)

673.32(15)

1587.28(11)

1285.2(2)

511.55(14)

520.83(9)

2

4

4

2

2

Dc (g cm )

1.866

2.021

1.940

2.112

2.479

F(000)

376

948

744

318

376

reflections/ unique

3534/ 1246

10180/ 2808

8095/ 2931

2679/ 1782

2697/ 1803

Rint

0.0185

0.0367

0.0277

0.0136

0.0097

3

V [Å ] Z –3

data/restraints/params

1246/ 0/ 101

2808/ 0/ 219

2931/ 0/ 190

1782/ 0/ 158

1803/ 0 /164

GOF on F2

1.118

1.097

1.099

1.118

1.088

R1, wR2 [I >2σ(I)]

0.0231, 0.0608

0.0333, 0.0740

0.0299, 0.0600

0.0376, 0.1020

0.0252, 0.0569

R1, wR2 (all data)

0.0260, 0.0618

0.0477, 0.0793

0.0403, 0.0642

0.0418, 0.1045

0.0264, 0.0578

largest diff. peak and

0.313, –0.312

0.398, –0.469

0.323, –0.360

1.061, –0.592

0.675, –0.529

–3

hole (e Å )

complex

6

7

8

9

formula

C42H24Cu7N20

C39H24Cu9N27

C12H8Cu2N6

C16H14Cu3N5

fw

1253.59

1442.71

363.32

466.94

cryst syst

triclinic

triclinic

monoclinic

triclinic

space group

Pī

Pī

C2/c

Pī

a (Å)

12.150(6)

8.848(5)

23.774(2)

7.6632(17)

b (Å)

13.704(7)

12.024(7)

6.7646(6)

8.3201(18)

c (Å)

15.398(7)

12.296(8)

17.0414(15)

14.958(3)

α (deg)

98.941(6)

89.376(8)

90

81.701(2)

β (deg)

107.594(6)

73.868(7)

98.9710(10)

79.626(2)

γ (deg)

109.176(6)

68.693(8)

90

67.423(2)

V [Å3]

2214.0(19)

1164.9(12)

2707.1(4)

863.2(3)

Z

2

1

8

2

Dc (g cm–3)

1.880

2.057

1.783

1.796

F(000)

1238

708

1440

464

reflections/ unique

13849/ 9804

5899 / 4017

8088/ 3079

3584/ 2612


Page 13 of 17

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


Rint

0.0463

0.0605

0.0345

0.0110

4017/ 0/ 340

3079/ 0/ 181

2612/ 0/ 217

0.922

1.321

1.037

1.029

0.0613, 0.1237

0.0762, 0.1480

0.0620, 0.1486

0.0326, 0.0800

data/restraints/params 9804/ 0/ 622 GOF on F

2

R1, wR2 [I >2σ(I)] R1, wR2 (all data)

0.0723, 0.1665

0.1167, 0.1615

0.0833, 0.1695

0.0373, 0.0839

largest diff. peak

1.777, –1.233

1.034, –0.965

1.229, –0.623

0.282, –0.560

–3

and hole (e Å )



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 17

For Table of Contents Use Only

Structural Diversity and Vibrational Spectra of Nine Cu(I)-Cyanide Metal-Organic Frameworks with in situ Generated N-Heterocyclic Ligands

Min Shao, Ming-Xing Li,* Zhao-Xi Wang, Xiang He and Heng-Hua Zhang

Nine porous MOFs were assembled by Cu(I)-cyanide and N-heterocyclic ligands. Partial N-heterocycles were in situ generated. Their structural features vary from 2D network, 3D framework, 3D 2-fold interpenetration, to 3D 3-fold interpenetration. Complex 1 is an intriguing 3D MOF with nanosized rectangular channel. Complex 7 is a 3D MOF with (3.4)-connected 5-nodal net containing btb guest molecule in rectangular channel. The characteristic ν(C≡N) stretching frequency in µ2-CN complexes correlates well with the Cu−CN bond distance. A decrease of about 6.7 cm−1 in ν(C≡N) corresponds to a 0.01 Å elongation of Cu−CN bond. These Cu(I)-cyanide complexes exhibit good thermally stable, and emit strong luminescence in 386–593 nm.


Page 15 of 17

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


Revised Table 1 Table 1. Crystallographic Data and Structure Refinement for Complexes 1–9 complex

1

2

3

4

5

formula

C13H8Cu2N6

C13H8Cu3N8O

C13H8Cu2N6

C8H4Cu2N7

C8H4Cu3N7

fw

375.35

482.89

375.33

325.26

388.80

cryst syst

monoclinic

monoclinic

orthorhombic

triclinic

triclinic

space group

P2/m

P21/n

P212121

Pī

Pī

a (Å)

5.2755(7)

7.8677(3)

7.7690(7)

7.9901(10)

7.8385(8)

b (Å)

15.4282(19)

8.0468(3)

7.8659(7)

8.9892(18)

8.8547(9)

c (Å)

8.2805(10)

25.1679(10)

21.031(2)

9.0317(11)

9.3060(10)

 (deg)

90

90

90

106.226(2)

62.7410(10)

(deg)

92.496(2)

95.013(2)

90

115.6990(10)

65.4500(10)

(deg)

90

90

90

103.579(2)

75.5090(10)

673.32(15)

1587.28(11)

1285.2(2)

511.55(14)

520.83(9)

2

4

4

2

2

1.866

2.021

1.940

2.112

2.479

F(000)

376

948

744

318

376

reflections/ unique

3534/ 1246

10180/ 2808

8095/ 2931

2679/ 1782

2697/ 1803

Rint

0.0185

0.0367

0.0277

0.0136

0.0097

Data/restraints/params 1246/ 0/ 101

2808/ 0/ 219

2931/ 0/ 190

1782/ 0/ 158

1803/ 0 /164

GOF on F2

1.118

1.097

1.099

1.118

1.088

R1, wR2 [I >2(I)]

0.0231, 0.0608

0.0333, 0.0740

0.0299, 0.0600

0.0376, 0.1020

0.0252, 0.0569

R1, wR2 (all data)

0.0260, 0.0618

0.0477, 0.0793

0.0403, 0.0642

0.0418, 0.1045

0.0264, 0.0578


0.313, –0.312

0.398, –0.469

0.323, –0.360

1.061, –0.592

0.675, –0.529

V

[Å3]

Z Dc (g

cm–3)

hole (e Å–3)

complex

6

7

8

9

formula

C42H24Cu7N20

C39H24Cu9N27

C12H8Cu2N6

C16H14Cu3N5

fw

1253.59

1442.71

363.32

466.94

cryst syst

triclinic

triclinic

monoclinic

triclinic

space group

Pī

Pī

C2/c

Pī

a (Å)

12.150(6)

8.848(5)

23.774(2)

7.6632(17)

b (Å)

13.704(7)

12.024(7)

6.7646(6)

8.3201(18)

c (Å)

15.398(7)

12.296(8)

17.0414(15)

14.958(3)

 (deg)

98.941(6)

89.376(8)

90

81.701(2)

(deg)

107.594(6)

73.868(7)

98.9710(10)

79.626(2)

(deg)

109.176(6)

68.693(8)

90

67.423(2)

V [Å3]

2214.0(19)

1164.9(12)

2707.1(4)

863.2(3)



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

Z

Page 16 of 17

2

1

8

2

1.880

2.057

1.783

1.796

F(000)

1238

708

1440

464

reflections/ unique

13849/ 9804

5899 / 4017

8088/ 3079

3584/ 2612

Rint

0.0463

0.0605

0.0345

0.0110


4017/ 0/ 340

3079/ 0/ 181

2612/ 0/ 217

GOF on F2

0.922

1.321

1.037

1.039

R1, wR2 [I >2(I)]

0.0613, 0.1237

0.0762, 0.1480

0.0620, 0.1486

0.0326, 0.0800

R1, wR2 (all data)

0.0723, 0.1665

0.1167, 0.1615

0.0833, 0.1695

0.0373, 0.0839

largest diff. peak

1.777, –1.233

1.034, –0.965

1.229, –0.623

0.282, –0.560

Dc (g

cm–3)

and hole (e Å–3)

Table 1. Crystallographic Data and Structure Refinement for Complexes 1–9 complex

1

2

3

4

5

formula

C13H8Cu2N6

C13H8Cu3N8O

C13H8Cu2N6

C8H4Cu2N7

C8H4Cu3N7

fw

375.35

482.89

375.33

325.26

388.80

cryst syst

monoclinic

monoclinic

orthorhombic

triclinic

triclinic

space group

P2/m

P21/n

P212121

Pī

Pī

a (Å)

5.2755(7)

7.8677(3)

7.7690(7)

7.990(1)

7.838(1)

b (Å)

15.428(2)

8.0468(3)

7.8659(7)

8.989(2)

8.855(1)

c (Å)

8.280(1)

25.168(1)

21.031(2)

9.032(1)

9.306(1)

 (deg)

90

90

90

106.226(2)

62.741(1)

(deg)

92.496(2)

95.013(2)

90

115.699(1)

65.450(1)

(deg)

90

90

90

103.579(2)

75.509(1)

V [Å3]

673.32(15)

1587.28(11)

1285.2(2)

511.55(14)

520.83(9)

Z

2

4

4

2

2

Dc (g cm–3)

1.866

2.021

1.940

2.112

2.479

F(000)

376

948

744

318

376

reflections/ unique

3534/ 1246

10180/ 2808

8095/ 2931

2679/ 1782

2697/ 1803

Rint

0.0185

0.0367

0.0277

0.0136

0.0097


2808/ 0/ 219

2931/ 0/ 190

1782/ 0/ 158

1803/ 0 /164

GOF on F2

1.118

1.097

1.099

1.118

1.088

R1, wR2 [I >2(I)]

0.0231, 0.0608

0.0333, 0.0740

0.0299, 0.0600

0.0376, 0.1020

0.0252, 0.0569

R1, wR2 (all data)

0.0260, 0.0618

0.0477, 0.0793

0.0403, 0.0642

0.0418, 0.1045

0.0264, 0.0578


0.313, –0.312

0.398, –0.469

0.323, –0.360

1.061, –0.592

0.675, –0.529

hole (e Å–3)


Page 17 of 17

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


complex

6

7

8

9

formula

C42H24Cu7N20

C39H24Cu9N27

C12H8Cu2N6

C16H14Cu3N5

fw

1253.59

1442.71

363.32

466.94

cryst syst

triclinic

triclinic

monoclinic

triclinic

space group

Pī

Pī

C2/c

Pī

a (Å)

12.150(6)

8.848(5)

23.774(2)

7.663(2)

b (Å)

13.704(7)

12.024(7)

6.7646(6)

8.320(2)

c (Å)

15.398(7)

12.296(8)

17.041(2)

14.958(3)

 (deg)

98.941(6)

89.376(8)

90

81.701(2)

(deg)

107.594(6)

73.868(7)

98.971(4)

79.626(2)

(deg)

109.176(6)

68.693(8)

90

67.423(2)

V [Å3]

2214.0(19)

1164.9(12)

2707.1(4)

863.2(3)

Z

2

1

8

2

Dc (g cm–3)

1.880

2.057

1.783

1.796

F(000)

1238

708

1440

464

reflections/ unique

13849/ 9804

5899 / 4017

8088/ 3079

3584/ 2612

Rint

0.0463

0.0605

0.0345

0.0110


4017/ 0/ 340

3079/ 0/ 181

2612/ 0/ 217

GOF on F2

0.922

1.321

1.037

1.029

R1, wR2 [I >2(I)]

0.0613, 0.1237

0.0762, 0.1480

0.0620, 0.1486

0.0326, 0.0800

R1, wR2 (all data)

0.0723, 0.1665

0.1167, 0.1615

0.0833, 0.1695

0.0373, 0.0839

largest diff. peak

1.777, –1.233

1.034, –0.965

1.229, –0.623

0.282, –0.560

and hole (e Å–3)


Structural Diversity and Vibrational Spectra of Nine Cu(I)-Cyanide

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