Exploring the Conformational Space of Bridge‐Substituted Dithienylcyclopentenes

Abstract

Fredersdorf, M.; Göstl, R.; Kolmer, A.; Schmidts, V.; Monecke, P.; Hecht, S.; Thiele, C.M. Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers)Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication Citation for published version (APA):Fredersdorf, M., Göstl, R., Kolmer, A., Schmidts, V., Monecke, P., Hecht, S., & Thiele, C. M. (2015). Exploring the conformational space of bridge-substituted dithienylcyclopentenes. Chemistry -A European Journal, 21(41), 14545-14554. DOI: 10.1002/chem.201501842 General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. [a, b] Robert Gçstl, [c, d] Andreas Kolmer, [a] VolkerS chmidts, [a] Peter Monecke, [b] StefanH echt,* [c] and ChristinaM.T hiele* [a] Abstract: Stimuli responsive compounds and materials are of high interesti ns ynthetic chemistry and materials science, with light being the most intriguing stimulus due to the possibility to remote control the physicochemical properties of am olecule or am aterial. There is ac onstant quest to design photoswitches with improveds witchinge fficiency and especially diarylethene-type switches promise photo cyclization quantum yields up to unity.H owever,o nly limited attention has been paid towards the influence of the solution conformationo nt he switchinge fficiency.H ere, we describe ad etailed NMR spectroscopic investigation on the conformational distribution of bridge-substituted dithienylcyclopentenes in solution.W ec ould discriminate between several photoactive and photoinactive as well as two diastereomorphous conformationsa nd show that the trends observed in the switching efficiencym atch the conformer populations obtainedf rom state of the a...

The Endeavor of Diarylethenes: New Structures, High Performance, and Bright Future

“…Other works toward bridge structure–activity relationship and functional ethene bridges were also noteworthy. Hecht and co‐workers and Shirinian and co‐workers, respectively, studied the space conformation of the diarylcyclopentenes with substituted bridges and the size effect of the ethene bridge. Ahn and co‐workers discovered a dihydro‐4H‐thieno[2,3‐b]thiopyran‐4‐one ethene bridged diarylethene, whose closed isomer was highly emissive.…”

Perspectives in the application of residual dipolar couplings in the structure elucidation of weakly aligned small molecules

“…The low natural abundance of the 13 C nucleus makes this type of interaction fairly difficult to measure experimentally though. There are only a few applications of INADEQUATE [93,94] as well as J-modulated ADEQUATE [95,96] type spectra known to the author, where such couplings were measured in an aligned molecule.…”

Conformational Analysis of an Antibacterial Cyclodepsipeptide Active against Mycobacterium tuberculosis by a Combined ROE and RDC Analysis

“…We have previously used the combination of NOE/ROE and RDC data for the investigationo ft he solutions tructure (including conformer populations for flexible compounds) of small organic compounds,p hotoswitchable compounds, and very recently,a lso of ah ighly efficient peptidec atalystu sed in kinetic resolution. [20][21][22][23] Although, for the former cases, the approach of probingc alculated structures with NMR data (NOE/ROE and RDC) was successful andc onformer ensemblest hat were in accordancew ith NOE/ROE and RDC data could be obtained with reasonable effort, the situation was more complicated for the peptidec atalyst. Am anualr efinement procedure, which involved as tep-wise construction procedure, had to be used to obtain an ensemble of conformers that was in accordance with both ROE and RDC data.…”

“…NOE/ROE and RDC data can be used to either probe a series of given structures, which have been obtained independently (e.g., by a conformational search)—the approach mainly taken in structure elucidation of (small) organic molecules—or as restraints in a refinement procedure—the approach mainly taken in bio(macro)molecular structure elucidation (as for example implemented in XPLOR‐NIH). We have previously used the combination of NOE/ROE and RDC data for the investigation of the solution structure (including conformer populations for flexible compounds) of small organic compounds, photoswitchable compounds, and very recently, also of a highly efficient peptide catalyst used in kinetic resolution . Although, for the former cases, the approach of probing calculated structures with NMR data (NOE/ROE and RDC) was successful and conformer ensembles that were in accordance with NOE/ROE and RDC data could be obtained with reasonable effort, the situation was more complicated for the peptide catalyst.…”