Stabilizing Two Classical Antiaromatic Frameworks: Demonstration of Photoacoustic Imaging and the Photothermal Effect in Metalla-aromatics†
Dr. Congqing Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorYuhui Yang
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorMing Luo
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorCaixia Yang
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)
Search for more papers by this authorJingjing Wu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorLina Chen
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorProf. Dr. Gang Liu
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)
Search for more papers by this authorProf. Dr. Tingbin Wen
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorCorresponding Author
Dr. Jun Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
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.htmSearch for more papers by this authorCorresponding Author
Prof. Dr. Haiping Xia
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
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.htmSearch for more papers by this authorDr. Congqing Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorYuhui Yang
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorMing Luo
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorCaixia Yang
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)
Search for more papers by this authorJingjing Wu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorLina Chen
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorProf. Dr. Gang Liu
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)
Search for more papers by this authorProf. Dr. Tingbin Wen
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
Search for more papers by this authorCorresponding Author
Dr. Jun Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
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.htmSearch for more papers by this authorCorresponding Author
Prof. Dr. Haiping Xia
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials ( i ChEM), 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
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.htmSearch for more papers by this authorThis research was supported by the 973 Program (Nos. 2012CB821600 and 2014CB744503), the NSFC (Nos. 21332002, 21172184, and 81422023) and the Program for New Century Excellent Talents in University (NCET-13-0511 and NCET-13-0502). We thank Prof. Xin Lu for helpful discussions.
Graphical Abstract
Two birds with one stone: Two classical antiaromatic molecules, cyclobutadiene and pentalene, were stabilized by introducing one metal fragment by a [2+2] cycloaddition reaction of osmapentalyne with alkynes. These metalla-aromatic molecules absorb broadly from the UV to the near-IR region and show significant photoacoustic and photothermal effects.
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.
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