Dual Function of ß-Hydroxy Dithiocinnamic Esters: RAFT Agent and Ligand for Metal Complexation.

The reversible addition-fragmentation chain-transfer (RAFT) process has become a versatile tool for the preparation of defined polymers tolerating a large variety of functional groups. Several dithioesters, trithiocarbonates, xanthates, or dithiocarbamates have been developed as effective chain transfer agents (CTAs), but only a few examples have been reported, where the resulting end groups are directly considered for a secondary use besides controlling the polymerization. Herein, it is demonstrated that ß-hydroxy dithiocinnamic esters represent a hitherto overlooked class of materials, which are originally designed for the complexation of transition metals but may as well act as reversible CTAs. Modified with a suitable leaving group (R-group), these vinyl conjugated dithioesters indeed provide reasonable control over the polymerization of acrylates, acrylamides, or styrene via the RAFT process. Kinetic studies reveal linear evolutions of molar mass with conversion, while different substituents on the aromatic unit has only a minor influence. Block extensions prove the livingness of the polymer chains, although extended polymerization times may lead to side reactions. The resulting dithiocinnamic ester end groups are still able to form complexes with platinum, which verifies that the structural integrity of the end group is maintained. These findings open a versatile new route to tailor-made polymer-bound metal complexes.

Activating a [FeFe] Hydrogenase Mimic for Hydrogen Evolution under Visible Light.

Inspired by the active center of the natural [FeFe] hydrogenases, we designed a compact and precious metal-free photosensitizer-catalyst dyad (PS-CAT) for photocatalytic hydrogen evolution under visible light irradiation. PS-CAT represents a prototype dyad comprising π-conjugated oligothiophenes as light absorbers. PS-CAT and its interaction with the sacrificial donor 1,3-dimethyl-2-phenylbenzimidazoline were studied by steady-state and time-resolved spectroscopy coupled with electrochemical techniques and visible light-driven photocatalytic investigations. Operando EPR spectroscopy revealed the formation of an active [FeI Fe0 ] species-in accordance with theoretical calculations-presumably driving photocatalysis effectively (TON≈210).

Synthesis, structural and antimicrobial studies of binary and ternary complexes of a new tridentate thiosemicarbazone.

A new thiosemicarbazone ligand was synthesized and characterized using spectroscopic techniques (UV-Vis and IR) and synchrotron x-ray powder diffraction. With M2+ = Mn2+, Zn2+ and Cd2+, coordination compounds of the type (M[L]2) were isolated. In the presence of sodium dithiocarbamate salts (NadiEtdtc.3H2O = sodium diethyldithiocarbamate trihydrate and Napipdtc = sodium piperidinedithiocarbamate), Zn2+ and Cd2+ were able to form ternary octahedral complexes where each metal binds a deprotonated (thiosemicarbazone) ligand, a monobasic dithiocarbamate ligand and a water molecule. In vitro biological evaluation tests of the free HL ligand and its metal complexes against selected fungal and bacterial cultures were performed. Compared with HL, the complexes displayed enhanced biological activities and ternary Zn (II) complexes displayed comparable antibacterial activities to the chloramphenicol standard.