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Silver(I)/Bipyrazole/Dicarboxylate Interpenetrated Coordination Networks: Spontaneous Chiral Resolution, Modulation of Topologies, Water Clusters, and Photoluminescences

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    Silver(I)/Bipyrazole/Dicarboxylate Interpenetrated Coordination Networks: Spontaneous Chiral Resolution, Modulation of Topologies, Water Clusters, and Photoluminescences
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    † Key Lab for Colloid and Interface Chemistry of Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, People’s Republic of China
    ‡ State Key Laboratory of Crystal Materials, Shandong University, Jinan, 250100, People’s Republic of China
    § College of Science, China University of Petroleum (East China), Qingdao, Shandong 266580, People’s Republic of China
    *E-mail: [email protected] (D.F.S.).
    *E-mail: [email protected] (D.S).
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    Crystal Growth & Design

    Cite this: Cryst. Growth Des. 2014, 14, 5, 2230–2239
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    https://doi.org/10.1021/cg401805x
    Published April 3, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    Seven novel silver(I) coordination networks with mixed flexible 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and C3–C9 aliphatic dicarboxylic acids, [Ag2(bpz)4(mal)·7H2O]n (1L and 1R), [Ag2(bpz)3(suc)]n (2), [Ag4(bpz)5(glu)2]n (3), [Ag4(bpz)5(adip)2]n (4), [Ag4(bpz)7(pim)2·12H2O]n (5), [Ag2(bpz)4(sub)·7H2O]n (6), and [Ag2(bpz)3(aze)·3.5H2O]n (7) (H2mal = malonic acid, H2suc = succinic acid, H2glu = glutaric acid, H2adip = adipic acid, H2pim = pimelic acid, H2sub = suberic acid, H2aze = azelaic acid), have been synthesized and structurally characterized by single-crystal X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). Single crystal X-ray diffraction analysis reveals that 1 crystallized into a pair of enantiomerically pure 3D 3-fold interpenetrated chiral SrSi2 networks (point symbol {103}) through spontaneous resolution in the absence of any chiral source. Complex 2 is a 3D 2-fold interpenetrated 3-connected uninodal dia-f network (point symbol {4·142}) without consideration of Ag···Ag interaction. Complexes 3 and 4 are similar 2D + 2D → 2D 63-hcb layer featuring 3-fold parallel interpenetration. Complex 5 is a 3D 3-fold interpenetrated 3,4-connected 3,4T1 network (point symbol {4·6·8}{4·62·83}). Complexes 6 and 7 are similar 2D + 2D → 2D fes layers (point symbol {4·82}) featuring 3-fold parallel interpenetration. In 1–7, structural diversity ranging from 2D hcb and fes layers to 3D chiral SrSi2, achiral dia-f, and 3,4T1 networks is modulated by dicarboxylates with alkyl chains of different lengths. Interestingly, a well-resolved octanuclear water cluster built from a chairlike (H2O)6 cluster and two water molecules dangling on two corners of it and a unusual seesaw-like pentanuclear water cluster is observed in the voids of 5 and 7, respectively. Furthermore, the solid-state photoluminescence properties of the 1–7 were investigated at 298 and 77 K.

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    Supporting Information

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    Crystallographic data in CIF format, powder X-ray diffraction (PXRD) patterns for 1–7, selected bond lengths and angles and hydrogen bond parameters for 1–7, crytallographic data for the randomly selected crystals of 1, summary of synthesis conditions for 1–7, and IR and UV–vis spectra of 1–7. This material is available free of charge via the Internet at http://pubs.acs.org. CIF files have also been deposited at the Cambridge Crystallographic Data Centre and may be obtained from http://www.ccdc.cam.ac.uk by citing deposition numbers 977473–977479 for 1–7.

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    Cite this: Cryst. Growth Des. 2014, 14, 5, 2230–2239
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    https://doi.org/10.1021/cg401805x
    Published April 3, 2014
    Copyright © 2014 American Chemical Society
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