Synthesis, Characterization, Sensing, and Coordination Properties of trans‐Homoporphodimethenes. Issue 24 (15th June 2018)

• Record Type: Journal Article
• Authors: Isar, Prosenjit; Rajeswara Rao, M.; Ravikanth, Mangalampalli
• Is Part Of: European journal of organic chemistry. Issue 24(2018)
• Page Start: 3095
• Page End: 3104
• Publication Date: 2018-06-15
• Subjects: Macrocycles -- Porphyrinoids -- Fluorescence -- Sensors -- Nitrogen heterocycles -- Sulfur heterocycles; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201800264
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Four different meso ‐substituted trans ‐homoporphodimethenes containing four five‐membered heterocycles connected through two sp 3 meso carbon atoms in a trans fashion and three sp 2 meso carbon atoms were synthesized in decent yields through the condensation reactions of 1 equiv. of an appropriate 2, 3‐dithienyl‐2‐butenediol with 1 equiv. of meso ‐( p ‐nitrophenyl)dipyrromethane under mild acid‐catalyzed conditions. All of the trans ‐homoporphodimethenes were characterized by HRMS as well as 1D and 2D NMR spectroscopy techniques, and the structure of one of the trans ‐homoporphodimethenes was determined by X‐ray crystallography. The crystal analysis indicated that the macrocycle is highly distorted owing to the presence of two meso sp 3 carbon atoms and attains a boat conformation. Anion‐sensing studies indicated that these macrocycles can be used as selective fluorescence turn‐on sensors for toxic CN – ions. The trans ‐homoporphodimethenes readily form BF2 complexes through treatment with BF3 · OEt2 in toluene in the presence of diisopropylethylamine at 70–80 °C for 4 h. The BF2 complexes of the trans ‐homoporphodimethenes showed fluorescence bands bathochromically shifted by ca. 80 nm compared with that of BODIPY (4, 4‐difluoro‐4‐bora‐3a, 4a‐diaza‐ s ‐indacene) as well as large Stokes shifts. Abstract : A series of meso ‐substituted trans ‐homoporphodimethenes are synthesized under simple reaction conditions, and their use as specific CN – ion sensors and coordinating ligands for BF2 complexes is demonstrated.