Abstract
We have directly determined the intramolecular electron transfer rate and revealed its mechanism in supramolecular complexes during CO2 photoreduction by time-resolved infrared spectroscopic measurements over a wide temporal range.
Highlights
$EVWUDFW :H KDYH GLUHFWO\ GHWHUPLQHG WKH LQWUDPROHFXODU HOHFWURQ WUDQVIHU UDWH DQG UHYHDOHG LWV PHFKDQLVP LQ VXSUDPROHFXODU FRPSOH[HV GXULQJ &2 SKRWRUHGXFWLRQ E\ WLPHUHVROYHG LQIUDUHG VSHFWURVFRSLF PHDVXUHPHQWV RYHU D ZLGH WHPSRUDO UDQJH.
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
)LJXUH D VKRZV H[DPSOHV RI 75,5 VSHFWUD IRU WKLV UHDFWLRQ LQ D FRPSOH[ ZLWK D &+ EULGJLQJ OLJDQG & 7KH WUDQVLHQW DEVRUSWLRQ EDQGV DW DQG FP DUH DVVLJQHG WR D FRPSOH[ ZLWK D UHGXFHG 5H XQLW 5X5Hā >@ 6LQFH WKH LQWHQVLWLHV RI WKHVH EDQGV FRUUHVSRQG WR WKH DPRXQW RI WKLV VSHFLHV ZH SORW RQH RI WKHP DV D IXQFWLRQ RI GHOD\ WLPH DV EODFN GRWV LQ )LJ E 7R UHSURGXFH WKLV WHPSRUDO SURILOH ZH VHW XS WKH UDWH HTXDWLRQV DFFRUGLQJ WR WKH VFKHPH LQ )LJ >@ 7KH UDWH FRQVWDQWV kG DQG kT ZHUH GHWHUPLQHG WR EH î V DQG î 0V EDVHG RQ WKH OXPLQHVFHQFH OLIHWLPHV RI WKH 5X XQLW DQG WKH GHSHQGHQFH RI WKH TXHQFKLQJ UDWH RQ WKH UHGXFWDQW FRQFHQWUDWLRQ 6WHUQ±9ROPHU SORW UHVSHFWLYHO\ ,Q DGGLWLRQ WKH UDWLR kHkH ZDV GHWHUPLQHG WR EH IURP WKH 899LV VSHFWUD IRU D SKRWRVWHDG\ VWDWH 7KXV RQO\ RQH SDUDPHWHU UHPDLQV XQGHWHUPLQHG WKH HOHFWURQ WUDQVIHU UDWH IURP WKH 5X XQLW WR WKH 5H XQLW kH :H FDUULHG RXW D OHDVWVTXDUHV ILW E\ VROYLQJ WKH UDWH HTXDWLRQV XVLQJ WKHVH UDWH FRQVWDQWV DQG GHWHUPLQHG WKH HOHFWURQ WUDQVIHU UDWH WR EH kH î V 7KH REWDLQHG FRQFHQWUDWLRQV RI 5X5Hā WKH FRPSOH[ ZLWK D UHGXFHG 5X XQLW 5Xā5H DQG WKH FRPSOH[ ZLWK D SKRWRH[FLWHG 5X XQLW 5X 5H DUH LQGLFDWHG E\ EOXH JUHHQ DQG UHG OLQHV LQ )LJ E UHVSHFWLYHO\ :H UHSHDWHG WKHVH PHDVXUHPHQWV DQG FDOFXODWLRQV IRU DQRWKHU IRXU VXSUDPROHFXODU FRPSOH[HV KDYLQJ GLIIHUHQW EULGJLQJ OLJDQGV
Summary
$EVWUDFW :H KDYH GLUHFWO\ GHWHUPLQHG WKH LQWUDPROHFXODU HOHFWURQ WUDQVIHU UDWH DQG UHYHDOHG LWV PHFKDQLVP LQ VXSUDPROHFXODU FRPSOH[HV GXULQJ &2 SKRWRUHGXFWLRQ E\ WLPHUHVROYHG LQIUDUHG VSHFWURVFRSLF PHDVXUHPHQWV RYHU D ZLGH WHPSRUDO UDQJH.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.