Regulation and Properties of Diversiform Cd(II) Supramolecular Complexes with a Bulky Naphthalene-Based Dicarboxyl Teeton and Different N-Donor Co-Ligands

A series or SIX Cd-11 coordination complexes have been prepared by using naphthalene-2.3-dicarboxylic acid (H(2)nde), an analogue of 1,2-benzenedicarboxylie acid (H(2)bdc), and different N-donor auxiliary co-ligands (chelating or bridging), namely, [Cd(nde)](infinity)(1),{[Cd-2(nde)(2)(2bpy)(2)(H2O)(2)](CH3OH)(0.5)}(2) (2),[Cd-2(nde)(2)(phen)(2)](infinity) (3), {[Cd(nde)(4hpy)(0.5)(H2O)(2)(H2O)},., (H2O)(2)](H2O)}(infinity)(4), {[Cd(nde)(abp)(H2O)](H2O)}(infinity)(5). and ([Cd(ndc)(bpp)(2)](H2O)3}(infinity) (6) (nde: = naphthalene-2,3-dicarboxylate, 2bpy = 2,2'-bipyridine, phen = 1.10-phenanthroline, 4bpy = 4,4'-bipyridine, abp = trans-4,4'-azobis(pyridine), and bpp = 1.3-bis(4-pyridyl) propane). The initial complex 1 shows a two-dimensional (2-D) (4(4).6(2)) coordination network. 2 and 3 possess tetranuclear and one-dimensional (I-D) structures due to the incorporation of auxiliary chelating co-ligands 2bpy and phen. respectively, which are further interlinked via secondary interactions such as hydrogen bonding and aromatic stacking to result in higher-dimensional supratmolecular networks. When the 4.4'-dipyridyl-type bridging co-ligands 4bpy, abp, and bpp (with different N,N'-donor separations of the molecular backbones from ca 7 10 angstrom) were used as the additional rod-like linkers, a 2-D(3.4)-connected (4(2).6)(4(2).6(3).8) layered coordination net 4 as well as a three-dimensional (3-D) coordination framework 5 with an unusual 4-connected irl topology (4(2).6(3).8) and a homochiral 3-D diamond (dia) network 6 were obtained. A structural comparison of these complexes with those based on the structurally related ligand 1,2-benzenedicarboxylate (tide) suggests that the extended pi-conjugated system of ndc with a different electronic nature and steric hulk plays an important role in the construction of supramolecular architectures for 1-6, which can also be well regulated by the different chelating or bridging.N-donor co-ligands. Moreover. complexes 1-6 exhibit strong solid-state luminescence emissions at room temperature, which mainly originate from the intraligand pi - pi* transitions of tide.