title: Stabilizing Two Classical Antiaromatic Frameworks: Demonstration of Photoacoustic Imaging and the Photothermal Effect in Metalla-aromatics.
abstract: Antiaromatic species are substantially less thermodynamically stable than aromatic moieties. Herein, we report the stabilization of two classical antiaromatic frameworks, cyclobutadiene and pentalene, by introducing one metal fragment through the first [2+2] cycloaddition reaction of a late-transition-metal carbyne with alkynes. Experimental observations and theoretical calculations reveal that the metal fragment decreases the antiaromaticity in cyclobutadiene and pentalene simultaneously, leading to air- and moisture-stable products. These molecules show broad absorption from the UV to the near-IR region, resulting in photoacoustic and photothermal effects for metalla-aromatic compounds for the first time. These results will encourage further efforts into the exploration of organometallic compounds for photoacoustic-imaging-guided photothermal therapy.
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Congqing
authors.initials: C
authors.lastname: Zhu
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Yuhui
authors.initials: Y
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Ming
authors.initials: M
authors.lastname: Luo
authors.affiliation: State Key Laboratory of Molecular Vaccinology and Molecular Diagnostics and Center for Molecular Imaging and Translational Medicine, School of Public Health, Xiamen University, Xiamen, 361102 (China).
authors.forename: Caixia
authors.initials: C
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Jingjing
authors.initials: J
authors.lastname: Wu
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Lina
authors.initials: L
authors.lastname: Chen
authors.affiliation: State Key Laboratory of Molecular Vaccinology and Molecular Diagnostics and Center for Molecular Imaging and Translational Medicine, School of Public Health, Xiamen University, Xiamen, 361102 (China).
authors.forename: Gang
authors.initials: G
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm.
authors.forename: Tingbin
authors.initials: T
authors.lastname: Wen
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm. jun.zhu@xmu.edu.cn.
authors.forename: Jun
authors.initials: J
authors.lastname: Zhu
authors.affiliation: State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China) http://junzhu.chem8.org/ http://chem.xmu.edu.cn/group/hpxia/index.htm. hpxia@xmu.edu.cn.
authors.forename: Haiping
authors.initials: H
authors.lastname: Xia
mesh_terms: D000480:Alkynes / Q000138:chemical synthesis / Q000737:chemistry; D061565:Cycloaddition Reaction; D003503:Cyclobutanes / Q000138:chemical synthesis / Q000737:chemistry*; D003517:Cyclopentanes / Q000138:chemical synthesis / Q000737:chemistry*; D003952:Diagnostic Imaging; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009992:Osmium / Q000737:chemistry*; D061088:Photoacoustic Techniques; D010789:Phototherapy
chemical_list: D000480:Alkynes; D003503:Cyclobutanes; D003517:Cyclopentanes; D009942:Organometallic Compounds; D009992:Osmium; C024646:pentalenene
keywords: antiaromaticity; cycloaddition; density functional calculations; metallacycles; osmium