Heteroatom-Containing Porphyrin Analogues.

The heteroatom-containing porphyrin analogues or core-modified porphyrins that resulted from the replacement of one or two pyrrole rings with other five-membered heterocycles such as furan, thiophene, selenophene, tellurophene, indene, phosphole, and silole are highly promising macrocycles and exhibit quite different physicochemical properties compared to regular azaporphyrins. The properties of heteroporphyrins depend on the nature and number of different heterocycle(s) present in place of pyrrole ring(s). The heteroporphyrins provide unique and unprecedented coordination environments for metals. Unlike regular porphyrins, the monoheteroporphyrins are known to stabilize metals in unusual oxidation states such as Cu and Ni in +1 oxidation states. The diheteroporphyrins, which are neutral macrocycles without ionizable protons, also showed interesting coordination chemistry. Thus, significant progress has been made in last few decades on core-modified porphyrins in terms of their synthesis, their use in building multiporphyrin arrays for light-harvesting applications, their use as ligands to form interesting metal complexes, and also their use for several other studies. The synthetic methods available in the literature allow one to prepare mono- and diheteroporphyrins and their functionalized derivatives, which were used extensively to prepare several covalent and noncovalent heteroporphyrin-based multiporphyrin arrays. The methods are also developed to synthesize different hetero analogues of porphyrin derivatives such as heterocorroles, heterochlorins, heterocarbaporphyrinoids, heteroatom-substituted confused porphyrins, and so on. This Review summarizes the key developments that have occurred in heteroporphyrin chemistry over the last four decades.

Panchromatic Light Capture and Efficient Excitation Transfer Leading to Near-IR Emission of BODIPY Oligomers.

All-BODIPY-based (BODIPY=boron-dipyrromethene) donor-acceptor systems capable of wide-band absorbance leading to efficient energy transfer in the near-IR region are reported. A covalently linked 3-pyrrolyl BODIPY-BODIPY dimer building block bearing an ethynyl group at the meso-aryl position is synthesized and coupled with three different monomeric BODIPY/pyrrolyl BODIPY building blocks with a bromo/iodo group under Pd(0) coupling conditions to obtain three covalently linked 3-pyrrolyl-BODIPY-based donor-acceptor oligomers in 19-29 % yield. The oligomers are characterized in detail by 1D and 2D NMR spectroscopy, high-resolution mass spectrometry, and optical spectroscopy. Due to the presence of different functionalized BODIPY derivatives in the oligomers, panchromatic light capture (300-725 nm) is witnessed. Fluorescence studies reveal singlet-singlet energy transfer from BODIPY monomer to BODIPY dimer leading to emission in the 700-800 nm range. Theoretical modeling according to the Förster mechanism predicts ultrafast energy transfer due to good spectral overlap of the donor and acceptor entities. Femtosecond transient absorption studies confirm this to be the case and thus show the relevance of the currently developed all-BODIPY-based energy-funneling supramolecular sytems with near-IR emission to solar-energy harvesting applications.

Synthesis and characterization of hexa-coordinated Sn(IV) complexes of meso-aryl dipyrrins.

Our successful synthesis of the first examples of Sn(IV) complexes of meso-aryl dipyrrins is reported. Sn(IV) dipyrrins are synthesized by treating meso-aryl dipyrrins with readily available SnCl2·2H2O in pyridine at reflux temperature and isolated as pure complexes by recrystallization. The X-ray structure revealed that the complex is hexa-coordinated and the Sn(IV) ion is coordinated to two dipyrrin units and two chlorides with overall appearance of a butterfly like structure. The complexes are stable in solution and characterized by spectral and electrochemical techniques.