Synthesis, structure, electronic characterization, and halogenation of gold(III) phlorin complexes

Pistner, Allen J.; Martin, Maxwell I.; Yap, Glenn P. A.; Rosenthal, Joel

doi:10.1142/s1088424621500565

Title: Synthesis, structure, electronic characterization, and halogenation of gold(III) phlorin complexes

Journal Article · Thu Jun 10 00:00:00 EDT 2021 · Journal of Porphyrins and Phthalocyanines

DOI:https://doi.org/10.1142/s1088424621500565· OSTI ID:1850731

Pistner, Allen J. ^[1]; Martin, Maxwell I. ^[1]; Yap, Glenn P. A. ^[1]; Rosenthal, Joel ^[1]

Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716, USA

The metalation chemistry of the phlorin, which is a non-aromatic tetrapyrrole macrocycle containing a single sp³-hybridized meso-carbon has remained underdeveloped, as compared to that of more traditional tetrapyrroles such as porphyrins, corroles and phthalocyanines. There have been few prior efforts to prepare metallophlorins, and those that have been reported have relied on either reduction or nucleophilic attack of parent metalloporphyrins, rather than direct metalation of freebase phlorin constructs. In this work, an alternate synthetic approach for preparation of gold(III) phlorin complexes that involves the first direct metalation of two different freebase phlorin derivatives (3H(Phl[Formula: see text] and 3H(Phl[Formula: see text] with AuBr₃to produce the stable and fully isolable gold(III) phlorin complexes Au(Phl[Formula: see text] and Au(Phl[Formula: see text] is reported. The first structural characterization of a metallophlorin bearing geminal dimethyl substituents at the sp³-hybridized meso-carbon via X-ray crystallography is also reported. In addition to the preparation of Au(Phl[Formula: see text] and Au(Phl[Formula: see text], the UV-vis absorption and redox properties of these two gold(III) phlorins in comparison to those of their freebase homologues is also detailed. Notably, the metallophlorins are characterized by panchromatic absorbance profiles and intense and broad bands that span the long-visible and into the near-IR regions, as well as two fully reversible oxidation and reduction waves as probed by cyclic voltammetry. Finally, the chlorination of Au(Phl[Formula: see text] using PhI(Cl[Formula: see text] was probed and it was found that this regioslective reaction generates monochlorinated (Au(Phl[Formula: see text]Cl)) and dichlorinated (Au(Phl[Formula: see text]Cl[Formula: see text] products, which were both structurally characterized by X-ray crystallography.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: SC0001234

OSTI ID:: 1850731

Journal Information:: Journal of Porphyrins and Phthalocyanines, Vol. 25, Issue 07n08; ISSN 1088-4246

Publisher:: World Scientific

Country of Publication:: United States

Language:: English

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