Five new coordination polymers, namely [Zn4(L)2(5-HIA)2]n·nH2O (1), [Cd2L(IPA)2]n·2nH2O (2), [Zn6L3(TPA)]n·4nH2O (3), [Zn8L4(TMA)8]n·nH2O (4) and [Co2L(TMA)2]n·3nH2O (5), have been hydrothermally prepared based on a tetrahedral linker, tetrakis(3-pyridyloxymethylene) methane (L), and different carboxylates (5-HIA = 5-hydroxyisophthalic acid, IA = isophthalic acid, TPA = terephthalic acid and TMA = trimesic acid). Complex 1 and 5 exhibit that L is sandwiched between two 2-D sheets, while 2 features a 3D structure with a (ZnL)n helix. Complex 3 exhibits a threefold interpenetration network. In 4, a 2D sheet is generated by intermolecular hydrogen bonds and is further linked into a 3D network. The thermal stability and photoluminescent properties of these polymers were investigated.Graphical abstractFive new coordination polymers have been synthesized and structurally characterized from the tetrahedral linker tetrakis(3-pyridyloxymethylene) methane (L) and different carboxylates. In addition, the effect of the position and amounts of aromatic carboxylic groups on the conformational diversity of L and the luminescence of the polymers have been discussed in detail.

To systematically investigate the influence of the positional isomeric effect on the structures of their complexes, we prepared two Zn(II) complexes [Zn4(L1)(PDC)4]·5H2O and [Zn2(L2)2(PDC)2]·3H2O based on a couple of tetrahedral linkers (L1 = tetrakis(4-pyridyloxymethylene)methane; L2 = tetrakis(3-pyridyloxymethylene)methane) in the presence of the carboxylate linkers (PDC = pyridine-2,6-dicarboxylic acid). Their structures and properties can be tuned by variable N-donor positions of the tetrahedral isomers. The X-ray crystallographic analysis demonstrate three-dimensional ones of complex 1 and two-dimensional ones of complex 2. This work indicates that isomeric effect of the couple of isomers play an important role in the construction of the Zn(II) complexes. In addition, their thermostability and photoluminescence are also reported in detail.Highlight► Two coordination polymers have been isolated under hydrothermal conditions. ► Differently oriented N-atoms in the tetrahedral isomers play a significant role in assembly of their final topologies and luminescence-tuning. ► The structural diversity is attributed to both positional isomeric effect of tetrahedral linkers and the steric hindrance of PDC used in the self-assembly process.

•Complex 1 and 2 are distinct structural characteristic: twofold interpenetrating diamondlike framework for 1 and a noncatenated structure based on infinite[Cu(SCN)]n chains for 2.•The symmetry matching of their secondary building unit (SBU) are of particular importance to control their degree of interpenetration.•Tetrakis(3-pyridyloxymethylene) methane (L) can be served as a good candidate for the construction of MOFs due to its specific tetrahedral configuration and flexible conformation.Two new coordination polymers based on CuX (X = SCN, I) and L have been successfully prepared by solvothermal reactions: [Cu4I4L] (1) and [Cu4(SCN)4L] (2) (L = tetrakis(3-pyridyloxymethylene)methane), exhibiting a doubly-fold interpenetrating diamondlike framework for 1 and a noncatenated structure with infinite[Cu(SCN)]n chains for 2. Their structural analysis shows the symmetry matching of their secondary building unit (SBU) can effectively control their degree of interpenetration.Graphical abstract