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Herein, a series of ionic mononuclear Cu(I) complexes, [Cu(phen)(bdppmapy)]Cl (1a), [Cu(phen)(bdppmapy)]Br (2a), [Cu(phen)(bdppmapy)]I (3a), [Cu(phen)(bdppmapy)]SCN (4a), [Cu(Dpq)(bdppmapy)]Cl (1b), [Cu(Dpq)(bdppmapy)]Br (2b), [Cu(Dpq)(bdppmapy)]I (3b) and [Cu(Dpq)(bdppmapy)]SCN (4b) {phen = [1,10]phenanthroline; Dpq = pyrazino[2,3-f][1,10]-phenanthroline; bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine} have been synthesized and characterized by using IR, NMR, elemental analysis, single crystal X-ray diffraction analysis, fluorescence spectroscopy methods, and UV-vis and terahertz (THz) time-domain absorption spectroscopy. Their crystal structures were elucidated by X-ray crystallography and their photophysical properties were investigated in detail. All the above complexes exhibit a 1D to 3D supramolecular structure which is linked together by intermolecular weak interaction forces and hydrogen bonds. By regulating ligands and anions, the emission wavelengths of these complexes are quite different in the range from 533 nm to 604 nm. Theoretical calculations and photophysical properties indicate that luminescence is derived from metal-to-ligand charge transfer (MLCT) excited states. In the meantime, the results of calculations show that the stabilization of the increased conjugation of the ligand-based π* orbital is ascribed to the observed bathochromic-shift in the MLCT transitions. [ABSTRACT FROM AUTHOR]

On the basis of the 3-(pyrazin-2-yl)-1H-pyrazole-5-carboxylic acid (H2L) ligand, four new polymers [Cu2(L2−)2] (1), [Zn3(L2−)2(H2O)4Cl2]n (2), [Pb(HL−)Cl]n (3), and {[Ni(L2−)(H2O)]·(H2O)}n (4) have been synthesized under solvothermal conditions. Polymer 1 possesses a discrete (0D) binuclear structure, which is further formed into a three-dimensional (3D) supramolecular structure by hydrogen bonding and π⋯π stacking interactions. Polymers 2 and 3 display one-dimensional (1D) infinite chain structures, which further extend into 3D supramolecular structures through hydrogen bonding interactions. Polymer 4 features two-dimensional (2D) layers which can form a 3D supramolecular architecture via interlayer hydrogen bonds. The ligand in the four polymers adopts different coordination modes for constructing versatile structures. Moreover, luminescence sensing study shows that polymer 2 is a promising luminescent sensor for the detection of Cu2+, Co2+ and Fe3+via drastic luminescence quenching in aqueous solution with high efficiency. The quenching constants KSV for Cu2+, Co2+ and Fe3+ are 6.35 × 103 M−1, 8.70 × 103 M−1 and 1.62 × 104 M−1, respectively. What's more, 1–4 with electrochemical luminescence (ECL) properties show high intensity in N,N-dimethylformamide (DMF) solution and high thermal stability. [ABSTRACT FROM AUTHOR]