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

Abstract

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.