Buthanapalli Ramakrishna

Facile synthesis of highly stable BF3-induced meso-tetrakis (4-sulfonato phenyl) porphyrin (TPPS4)-J-aggregates: structure, photophysical and electrochemical properties

We report herein, a novel method for the formation of highly stable BF3-induced J-aggregates by interaction between meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4) and BF3O(C2H5)2. The aggregates were characterized by NMR (1H, 11B and 19F), optical absorption, cyclic voltammetry, FT-IR and fluorescence spectroscopic techniques. TPPS4 readily forms a 1 : 2 adduct with BF3 which further converts into BF3-induced TPPS4 aggregates whose spectroscopic properties strongly depend on the concentration of BF3. The optical absorption spectrum shows the formation of J-type aggregates with an apparent association constant (logKapp) of 4.2 ± 0.1. The steady state emission shows formation of 1 : 2 (TPPS4–BF3) adducts at ∼685 nm and J-aggregates exhibit emission at 732 nm with a red shift of ∼17 nm in comparison to J-aggregates of TPPS4 with TFA. The fluorescence lifetime of TPPS4 : BF3 (1 : 2) adducts exhibits ∼3.68 ns and aggregates show a lifetime of 4.32 ± 0.2 ns with major abundance. NMR study reveals that proton transfer occurs from pyrrole N–H to the SO3− groups and J-aggregates were stabilized by strong intermolecular hydrogen bonding interaction between N2–BF2 and SO3H. Cyclic voltammetry shows a decrease in the reduction peak current along with a change in the peak potentials for the aggregates. The PXRD pattern of the aggregates exhibits orthorhombic structure with interplanar distance of 4.87 A. The variations in unusual stability, photophysical, electrochemical properties and nature of the aggregates were rationalized with aggregates of TPPS4 dication.

Amide-Functionalized Chalcogen-Bridged Flexible Tetranuclear Rhenacycles: Synthesis, Characterization, Solvent Effect on the Structure, and Guest Binding

The synthesis of flexible rhenium(I)-based amide-functionalized chalcogen-bridged tetranuclear metallacycles of general formula [{(CO)3Re(μ-ER)2Re(CO)3}2(μ-L)2] (1–8) was achieved by treating rhenium carbonyl with dialkyl/diaryl chalcogenide (RE–ER; E = S and Se) in the presence of ditopic flexible or semiflexible pyridyl ligand with amide functionality (L = N,N′-bis(4-pyridylcarboxamide)-1,2-ethane (bpce) and N,N′-bis(4-(4-pyridylcarboxamide)phenyl)methane (bpcpm)). Compounds 1–8 were formed by multicomponent self-assembly under one-pot reaction conditions via oxidative addition of dialkyl/diaryl chalcogenide to rhenium carbonyl with pyridyl ligands. The resultant metallacyclophanes were characterized using elemental analyses, infrared, ultraviolet–visible, and NMR spectroscopic techniques. Metallacyclophanes 1–3 and 7 were structurally characterized by single-crystal X-ray diffraction methods. The solvent-induced structural change of flexible tetranuclear metallacyclophane 2 was demonstrated by crystallizing 2 in dichloroethane and dimethylformamide. Molecular recognition capabilities of 2 and 7 were studied with few aromatic compounds containing ethereal linkages.

CCDC 1537239: Experimental Crystal Structure Determination

Related Article: B. Raghavendra, K. Bakthavachalam, Buthanapalli Ramakrishna, N. Dastagiri Reddy|2017|Organometallics|||doi:10.1021/acs.organomet.7b00617

CCDC 1537020: Experimental Crystal Structure Determination

Related Article: B. Raghavendra, K. Bakthavachalam, Buthanapalli Ramakrishna, N. Dastagiri Reddy|2017|Organometallics|36|4005|doi:10.1021/acs.organomet.7b00617