Quantitative Vibrational Dynamics of the Metal Site in a Tin Porphyrin: An IR, NRVS, and DFT Study

• Published in: Inorganic chemistry Vol. 52; no. 17; pp. 9948 - 9953
• Main Authors: Leu, Bogdan M, Zgierski, Marek Z, Bischoff, Christian, Li, Ming, Hu, Michael Y, Zhao, Jiyong, Martin, Steve W, Alp, Esen Ercan, Scheidt, W. Robert
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.09.2013
• Subjects: Metalloporphyrins - chemistry; Models, Molecular; Quantum Theory; Spectrophotometry, Infrared; Tin - chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic401152b

We used a newer, synchrotron-based, spectroscopic technique (nuclear resonance vibrational spectroscopy, NRVS) in combination with a more traditional one (infrared absorption, IR) to obtain a complete, quantitative picture of the metal center vibrational dynamics in a six-coordinated tin porphyrin. From the NRVS 119Sn site-selectivity and the sensitivity of the IR signal to 112Sn/119Sn isotope substitution, we identified the frequency of the antisymmetric stretching of the axial bonds (290 cm–1) and all the other vibrations involving Sn. Experimentally authenticated density functional theory (DFT) calculations aid the data interpretation by providing detailed normal mode descriptions for each observed vibration. These results may represent a starting point toward the characterization of the local vibrational dynamics of the metallic site in tin porphyrins and compounds with related structures. The quantitative complementariness between IR, NRVS, and DFT is emphasized.