Blue photoluminescent zinc coordination polymers with supertetranuclear cores

Abstract

First published as an Advance Article on the webTwo photoluminescent two-and three-dimensional coordination polymers consisting of Zn 4 O [or Zn 4 (OH) 2 ] cores, dicarboxylate (isophthalate or fumarate) and 4,4A-bipyridine ligands as building blocks have been hydrothermally synthesized and structurally characterized.The construction of supramolecular architectures are currently of great interest owing to their intriguing network topologies and potential functions as new classes of materials. 1 Polynuclear d 10 metal (Cu I , Ag I , Au I , Zn II or Cd II ) complexes have been found to exhibit intriguing structural and photoluminescent properties. 2-5 We have been pursuing synthetic strategies for non-interpenetrating open frameworks with variable cavities or channels using simple units as building blocks. 6 We now extend to work towards extended networks based on metal clusters as building blocks, and report here the preparation and crystal structures of two novel coordination polymers constructed by zinc cluster cores, 4,4A-bipyridine (4,4A-bpy) and dicarboxylate ligands, namely [Zn 4 O(ip) 3 (4,4A-bpy)] (ip = isophthalate) 1 and [Zn 4 (OH) 2 (fa) 3 (4,4A-bpy) 2 ] (fa = fumarate) 2.

Directed anisotropy in bis(acetato-κ2O,O′)diaquazinc(II) at 110 and 250 K

“…The bidentate mode, in which both carboxylate O atoms coordinate to the same Zn centre and form a four-membered Zn-O-C-O ring, leads to an extremely strained situation, with Zn-O-C angles close to 90 instead of the optimal 120 and O-Zn-O angles close to 60 instead of the octahedral 90 (Tables 1 and 3 (Dietzel et al, 2006) and 2.639 (4) Å (Tao et al, 2000). Crystal structures of bidentate carboxylate groups with tetrahedral Zn centres are unknown.…”

Crystal structure of 4,4'-bipyridine dihydrate, C10H8N2·2H2O, C10H12N2O2

“…This value is similar to that of 41.6(1)°determined for 4,4'-bipyridine dihydrate [4]. In contrast, the corresponding angles of anhydrous 4,4'-bipyridine, are 18.5(1) and 34.9(1)° [7].I ntermolecular O-H···N and O-H···O hydrogen bonds lead to the infinite chain structure formed by 4,4'-bipyridine and H 2 Omolecules, which is just similar to those in the compound of 4,4'-bipyridine dihydrate [4].Finally it should be mentioned that there is am etrical similarity between the low-temperature structure of bipy·2H 2 …”

“…Due to the two Natoms in the connected six-membered rings, bipy is able to coordinate to multifarious metals [1][2][3]. During our attempts to synthesize Ag(I) complexes of 1,4-bis(diphenyl phosphino)butane and bipy,w eo btainedc rystals of an ew polymorph of C 10 H 8 N 2 ·2H 2 O [4].Polymorphism can be found in any crystalline material including polymers,m inerals and elemental solids.…”

Crystal structure of bisnitrate-bis(1-(4-((1H-imidazol-1yl)methyl)- benzyl)-1H-imidazole)cadmium(II), [Cd(NO3)2(C14H14N4)2]n

“…Over the past two decades, different classes of coordination polymers have been successfully designed and synthesized. Recently, bridging ligands containing No r/and O, for examplemultidentate aromatic polycarboxylate [4][5][6][7][8], have been widely used forsyntheses of coordination polymers of transition metals [9][10]. In the title crystal structure, there are one cadmium ion, two nitrate ions and two 1-(4-((1H-imidazol-1-yl)methyl)benzyl)-1H-imidazolem olecules per asymmetric unit.…”