Light-induced self-assemblies suitable for photodimerization and their light-induced [2+2] cycloaddition: Light as a control factor of crystal growth

Jung In Poong, Hyo Geun Koo, Hyun Min Park, Seung Pyo Jang, Yu Jin Lee, Cheal Kim, Sung Jin Kim, Youngmee Kim

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5 Scopus citations

Abstract

The reaction of Cd(NO3)2 and CF3COONH 4 with bpe (trans-1,2-(bis(4-pyridyl)ethene)) ligands was investigated for a light-induced solid-state [2+2] cycloaddition reaction. The three structures (1 [Cd(bpe)2(CF3COO)2] n, 2 [Cd(bpe)2(NO3)2]n, and 3 [Cd(NO3)(μ-NO3)(H2O)(bpe) 1.5]n) formed in light while only compound 1 (or 1-dark) was formed in the dark. All three compounds were completely transformed to the final [2+2] cycloaddition products containing rctt-tetrakis(4-pyridyl) cyclobutane (rctt-tpcb; rctt means regional cis, trans, and trans of the four pyridyl groups attached to the cyclobutane ring) in solution under a natural light after 4 weeks. Among the final products, only one 3-D structure (4 [{Cd(rctt-tpcb)2(NO3)2}{Cd(rctt-tpcb) 2(OH)2}]n) with a good crystallinity was determined by the X-ray diffraction technique. These observations were also in line with the spectroscopic results such as 1H NMR. Meanwhile, 3 was also prepared separately and exposed to natural light. X-ray and NMR studies showed that 3 was completely transformed to 4 containing rctt-tpcb by a light-induced cycloaddition reaction for the 4 weeks. The reaction progress was further monitored by fluorescent spectroscopy. 1-dark also underwent the solid-state [2+2] cycloaddition under the natural light over four weeks.

Original languageEnglish
Pages (from-to)605-611
Number of pages7
JournalInorganica Chimica Acta
Volume376
Issue number1
DOIs
StatePublished - 1 Oct 2011

Bibliographical note

Funding Information:
We gratefully acknowledge the financial support from the Korea Ministry Environment “ET-Human Resource Development Project;” Korean Science & Engineering Foundation ( R01-2008-000-20704-0 and 2009-0074066 ); Converging Research Center Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology ( 2009-0082832 ); and SRC program of NRF through the Center for Intelligent Nano-Bio Materials at Ewha Womans University ( 20090063004 ).

Keywords

  • Coordination polymers
  • Photodimerization
  • Self-assembly
  • X-ray crystal structures

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