Tribute to Professor Dr Michael Hanack

Nanocrystalline Axially Bridged Iron Phthalocyanine Polymeric Conductor: (μ-Thiocyanato)(phthalocyaninato)iron(III)

“…The versatility of MPc as building blocks for molecular conductors can further be utilized through the attachment of axial ligands to its metal center (octahedral) which would result in either slip-stacked arrangement [2] or a "shishkebab" polymeric form [3][4][5]. The electrical conduction of slip-stacked MPc units highly depends on its arrangement in solid-state which is mainly due to the effectiveness of its intermolecular -orbital overlap/interaction (Scheme 2(a)) [6,7], while the polymerization of MPcL 2 through axialligand (bidentate) bridge extends the highly delocalizedelectron of the macrocycle by forming linear -electron containing organic molecules, resulting in additional stacking dimension for the -electron transport, and thereby minimizing dependence on solid-state orientation (Scheme 2(b)) [8].…”

Synthesis of Ruthenium(III) Phthalocyanine with Di-axial Bromo Ligands - A Promising Molecular Conductor with Giant Negative Magnetoresistance

“…Ruthenium phthalocyanine and its derivatives have been recognized to have promising solid-state properties, however, this class of compounds has not been studied in much detail because their labile nature made them very difficult to synthesize through the years 7,8 . The preparation of Ru III (Pc)L2, particularly Ru III (Pc)Br2, could result in a magnetic molecular conductor system that could achieve greater GNMR or could attain GNMR at significantly lower magnetic field than its already acceptable Fe III (Pc)L2 homologue.…”

Crystal Structure of Ruthenium Phthalocyanine with Diaxial Monoatomic Ligand: Bis(Triphenylphosphine)Iminium Dichloro(Phthalocyaninato(2‐))Ruthenium(III)

“…Electronic structure calculations using two state-averaged complete active space multicon�gurational SCF method (active space orbitals: Pc-, Feand ; Stuttgart-Köln ECP + DZ basis) resulted in ΔE (orbital energy difference between / and HOMO; intensity of the -d interaction) of 8.5450 eV, 8.3839 eV, and 7.8655 eV for L = Br, Cl, and CN, respectively. Using the same theoretical calculation framework to Ru III (Pc)L 2 , which is electronically isostructural with the Fe III (Pc)L 2 species, the 5 homologue system resulted in a remarkable increase of around two-fold in the -d interactions across all Ru III (Pc)L 2 species (L: CN = 3.7518 eV, Cl = 3.8419 eV, Br = 3.9411 eV). Given that the intensity of the unique intramolecular -d interaction as the origin of the varying anisotropic GNMR in M III (Pc)L 2 , thus the importance of the synthesis of ruthenium(III) phthalocyanine with linear axial ligands.…”

“…e synthesis of crystalline ruthenium phthalocyanine Ru(Pc) complexes has long been a challenge in phthalocyanine chemistry. Even upon the report of pure Ru(Pc) synthesis more than three decades ago, the ambiguities of its solid-state/materials science still remain as only very few crystal structures of 6-coordinated axially ligated Ru(Pc) complexes have been reported [5,6]. However, these Ru(Pc) complexes have bulky and/or unsymmetrical axial ligands unsuitable for structure-property correlation studies.…”