Syntheses, Structures, and Properties of a Series of Multidimensional Metal–Organic Polymers Based on 3,3′,5,5′-Biphenyltetracarboxylic Acid and N‑Donor Ancillary Ligands

Hydrothermal reactions of aromatic 3,3′,5,5′-biphenyltetracarboxylic acid (H₄bpt) and the transitional metal cations in the presence of rigid or flexible N-donor ancillary ligands afford nine novel coordination polymers, namely, [M­(H₂bpt)­(Hpptp)]_<i>n</i> (M = Mn (<b>1</b>), Fe (<b>2</b>), Co (<b>3</b>), and Zn (<b>4</b>)), [Mn₂(bpt)­(Hpptp)₂]_<i>n</i> (<b>5</b>), {[Zn₃(Hbpt)­(bpt)­(H₂O)₂]­[(4,4′-H₂bmib)_0.5]·H₂O}_<i>n</i> (<b>6</b>), {[Cu­(bpt)_0.5(4,4′-bimbp)]·H₂O}_<i>n</i> (<b>7</b>), {[Co­(H₂bpt)­(2,7-dfo)]·H₂O}_<i>n</i> (<b>8</b>), and {[Ni₂(bpt)­(4,4′-bibp)_2.5(H₂O)]·3­(H₂O)}_<i>n</i> (<b>9</b>) (Hpptp = 2-(3-(4-(pyridin-4-yl)­phenyl)-1<i>H</i>-1,2,4-triazol-5-yl)­pyridine; 4,4′-bmib = 4,4′-bis­(2-methylimidazol-1-yl)­benzene; 4,4′-bimbp = 4,4′-bis­(imidazol-1-ylmethyl)­biphenyl; 2,7-dfo = 2,7-di­(imidazo-1-ly)-9<i>H</i>-fluoren-9-one; 4,4′-bibp = 4,4′-bis­(imidazol)­biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Complexes <b>1</b>–<b>4</b> are isomorphism and feature a similar 2-fold interpenetrating 2D helical double layer, which is further extended via the interlayer π···π interactions into a 3D supramolecular structure. Complex <b>5</b> displays a pillared-layer 3D porous network with a (6².8)₂(6².8².10²) topology. Compound <b>6</b> shows an unprecedented 3D host-framework consisting of Zn₆ clusters and exhibits a novel 3D (5,5,5,6,9)-connected topological net with the Schläfli symbol of (4¹⁰.6⁵)­(4¹⁹.6¹⁶.8)­(4⁶.6⁴)­(4⁷.6³)₂. The topology of <b>7</b> is an unprecedented binodal (4,4)-connected 3D network with the Schläfli symbol of (6².8⁴)­(4².8²)₂. Complex <b>8</b> exhibits a 3D (6⁶) structure with left- and right-handed helical chains arranged alternately. Complex <b>9</b> is a novel trinodal (4,4,5)-connected 3D framework with the Schläfli symbol of (6⁴.8²)­(6⁵.8)­(6⁸.8²). To the best of our knowledge, the 3D frameworks with (5,5,5,6,9)-connected net for <b>6</b>, binodal (4,4)-connected for <b>7</b>, and trinodal (4,4,5)-connected for <b>9</b> have never been documented to date. Moreover, the luminescent properties of <b>4</b> and <b>6</b> have been investigated