Cyanide-bridged complexes based on dinuclear Cu(Ⅱ)-M(Ⅱ) [M=Pb and Cu] building blocks: Synthesis, crystal structures and magnetic properties

Four cyanide-bridged heterometallic complexes { [CuPb（L1）][FenI（bpb）（CN）2] }2-（C104）2.2H20.2CH3CN （1）, { [CuPb（LI）]2[FeII （CN）6]（HzO）z}＇10H20 （2）, {[Cu2（L2）][Fent（bpb）（CN）2]2}＇2H20＇2CH3OH （3） and {[Cu2（L2）]3[FeIII（CN）6]z（H20）2}-10H20 （4） have been synthesized by treating K[Fem（bpb）（CN）2] [bpb2-=l,2-bis（pyridine-2-carboxamido）benzenate] and K3[Feln（CN）]6 with dinuc[ear compartmental macrocyclic Schiff-base complexes [CuPh（LI）].（C104）2 or [Cu2（L2）]-（CIO4）2, in which H2LJ was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2：1：1 and H2L2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1：1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [Fem（bpb）（CN）2]- and [CuPb（L＋）]2＋ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe（CN）6]4- anion sandwiched in two [CuPu（L1）]2＋ cations, and the pentanuclear moieties are further connected by the hydro- gen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cuz（L2）]2＋ segment and two terminal cyanide-containing blocks [Fetn（bpb）（CN）2]-. Octanuclear compound 4 is built from two [Fe（CN）6]3- anions sandwiched in the three [Cu2L2]2＋ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.

Density functional theory study on organic semiconductor for field effect transistors: Symmetrical and unsymmetrical porphyrazine derivatives with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene moieties

Density functional theory (DFT) calculations were carried out to investigate the organic field effect transistor (OFET) performance of the symmetrical metal-free tetrakis (1,2,5-thiadiazole) porphyrazine (S4)PzH2 and tetrakis (1,4-diamyloxybenzene) (A4)PzH2 as well as the low-symmetry metal-free porphy- razine with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene groups in the ratio 2:2 (cis) and 1:3, that is, (cis-S2A2)PzH2 and (SA3)PzH2, (S = 1,2,5-thiadiazole ring, A = annulated 1,4-diamyloxy-benzene ring, Pz = porphyrazine) in terms of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy, ionization energy (IE), electron affinity (EA), and their reorganization energy (λ) during the charge-transport process. On the basis of Marcus electron transfer theory, electronic couplings (V) and field effect transistor (FET) properties for the four compounds with known crystal structure have been calculated. The electron transfer mobility (μ -) is revealed to be 0.056 cm2·V-1·s-1 for (S4)PzH2. The hole transfer mobility (μ+) is 0.075, 0.098, and 8.20 cm2·V-1·s-1 for (cis-S2A2)PzH2, (SA3)PzH2, and (A4)PzH2, respectively. The present work represents the theoretical effort towards understanding the OFET properties of symmetrical and unsymmetrical porphyrazine derivatives with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene.