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Design of diethynyl porphyrin derivatives with high near infrared fluorescence quantum yields

Department of Chemistry, 231 South 34th Street, University of Pennsylvania, Philadelphia, PA 19104-6323, USA

Current address: Optical Sciences Division, U.S. Naval Research Laboratory, Washington, DC 20375, USA and Sotera Defense Solutions, Inc., Columbia, MD 21046, USA.

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and

Michael J. Therien

Department of Chemistry, French Family Science Center, 124 Science Drive, Duke University, Durham, NC 27708-0346, USA

Corresponding author, tel: +1 919-660-1670.

SPP full member in good standing.

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https://doi.org/10.1142/S1088424614501107Cited by:12 (Source: Crossref)

Abstract

A design strategy for (porphinato)zinc-based fluorophores that possess large near infrared fluorescence quantum yields is described. These fluorophores are based on a (5,15-diethynylporphinato)zinc(II) framework and feature symmetric donor or acceptor units appended at the meso-ethynyl positions via benzo[c][1,2,5]thiadiazole moieties. These (5,15-bis(benzo[c][1′,2′,5′]thiadiazol-4′-ylethynyl)-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (4), (5,15-bis[4′-(N,N-dihexylamino) benzo[c][1′,2′,5′]thiadiazol-7′-ylethynyl]-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (5), (5,15-bis([7′-(4″-n-dodecyloxyphenylethynyl)benzo[c][1′,2′,5′]thiadiazol-4′-yl]ethynyl)-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (6), (5,15-bis([7′-([7″-(4″ ′-n-dodecyloxyphenyl)benzo[c][1″,2″,5″]thiadiazol-4″-yl]ethynyl)benzo[c][1′,2′,5′]thiadiazol-4′-yl]ethynyl)-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (7), 5,15-bis ([7′-(4″-N,N-dihexylaminophenylethynyl)benzo[c][1′,2′,5′]thiadiazol-4′-yl]ethynyl)-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (8), and (5,15-bis([7′-(4″-N,N-dihexylaminophenylethenyl)benzo[c][1′,2′,5′]thiadiazol-4′-yl]ethynyl)-10,20-bis[2′,6′-bis(3″,3″-dimethyl-1″-butyloxy)phenyl]porphinato)zinc(II) (9) chromophores possess red-shifted absorption and emission bands that range between 650 and 750 nm that bear distinct similarities to those of the chlorophylls and structurally related molecules. Interestingly, the measured radiative decay rate constants for these emitters track with the integrated oscillator strengths of their respective x-polarized Q-band absorptions, and thus define an unusual family of high quantum yield near infrared fluorophores in which emission intensity is governed by a simple Strickler–Berg dependence.

Dedicated to Professor Shunichi Fukuzumi on the occasion of his retirement.

Keywords:

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References

R. Weissleder , Nat. Biotechnol. 19 , 316 ( 2001 ) . Crossref, Web of Science, Google Scholar
R. Weissleder and V. Ntziachristos , Nat. MEd. 9 , 123 ( 2003 ) . Crossref, Web of Science, Google Scholar
C. Bremer , V. Ntziachristos and R. Weissleder , Eur. Radiol. 13 , 231 ( 2003 ) . Crossref, Web of Science, Google Scholar
J. V. Frangioni , Curr. Opin. Chem. Biol. 7 , 626 ( 2003 ) . Crossref, Web of Science, Google Scholar
S. A. Hilderbrand and R. Weissleder , Curr. Opin.Chem. Biol. 14 , 71 ( 2010 ) . Crossref, Web of Science, Google Scholar
M. V. Martínez-Díaz , G. de la Torre and T. Torres , Chem. Commun. 46 , 7090 ( 2010 ) . Crossref, Web of Science, Google Scholar
Y. Liu et al. , Chem. Commun. 47 , 4010 ( 2011 ) . Crossref, Web of Science, Google Scholar
Y.-C. Chang et al. , Chem. Commun. 47 , 8910 ( 2011 ) . Crossref, Web of Science, Google Scholar
S. Mathew et al. , Nature Chem. 6 , 242 ( 2014 ) . Crossref, Web of Science, Google Scholar
F. D'Souza et al. , J. Am. Chem. Soc. 134 , 654 ( 2012 ) . Crossref, Web of Science, Google Scholar
V. Balzani , A. Credi and M. Venturi , ChemSusChem 1 , 26 ( 2008 ) . Crossref, Web of Science, Google Scholar
J. Roncali , Chem. Rev. 97 , 173 ( 1997 ) . Crossref, Web of Science, Google Scholar
H. A. M. van Mullekom et al. , Mater. Sci. Eng. 32 , 1 ( 2001 ) . Crossref, Web of Science, Google Scholar
A. Tsuda and A. Osuka , Science 293 , 79 ( 2001 ) . Crossref, Web of Science, Google Scholar
K. Kiyose , H. Kojima and T. Nagano , Chem. Asian J. 3 , 506 ( 2008 ) . Crossref, Web of Science, Google Scholar
J. O. Escobedo et al. , Curr. Opin. Chem. Biol. 14 , 64 ( 2010 ) . Crossref, Web of Science, Google Scholar
G. Qian and Z. Y. Wang , Chem. Asian J. 5 , 1006 ( 2010 ) . Crossref, Web of Science, Google Scholar
S. Luo et al. , Biomaterials 32 , 7127 ( 2011 ) . Crossref, Web of Science, Google Scholar
H. Mori , T. Tanaka and A. Osuka , J. Mater. Chem. C 1 , 2500 ( 2013 ) . Crossref, Web of Science, Google Scholar
W. Zhao and E. M. Carreira , Angew. Chem. Int. Ed. 44 , 1677 ( 2005 ) . Crossref, Web of Science, Google Scholar
K. Umezawa et al. , J. Am. Chem. Soc. 130 , 1550 ( 2008 ) . Crossref, Web of Science, Google Scholar
S. J. Strickler and R. A. Berg , J. Chem. Phys. 37 , 814 ( 1962 ) . Crossref, Web of Science, Google Scholar
R. Englman and J. Jortner , Mol. Phys. 18 , 145 ( 1970 ) . Crossref, Web of Science, Google Scholar
M. Gouterman , J. Mol. Spectrosc. 6 , 138 ( 1961 ) . Crossref, Web of Science, Google Scholar
O. S. Finikova , A. V. Cheprakov and S. A. Vinogradov , J. Org. Chem. 70 , 9562 ( 2005 ) . Crossref, Web of Science, Google Scholar
J. Nakamura et al. , Heterocycles 80 , 1165 ( 2010 ) . Crossref, Web of Science, Google Scholar
N. K. S. Davis , A. L. Thompson and H. L. Anderson , Org. Lett. 12 , 2124 ( 2010 ) . Crossref, Web of Science, Google Scholar
N. K. S. Davis , A. L. Thompson and H. L. Anderson , J. Am. Chem. Soc. 133 , 30 ( 2011 ) . Crossref, Web of Science, Google Scholar
V. V. Diev et al. , J. Org. Chem. 77 , 143 ( 2012 ) . Crossref, Web of Science, Google Scholar
K. Sauer , J. R. L. Smith and A. J. Schultz , J. Am. Chem. Soc. 88 , 2681 ( 1966 ) . Crossref, Web of Science, Google Scholar
J. S. Connolly , E. B. Samuel and A. F. Janzen , Photochem. Photobiol. 36 , 565 ( 1982 ) . Crossref, Web of Science, Google Scholar
L. S. Forster and R. Livingston , J. Chem. Phys. 20 , 1315 ( 1952 ) . Crossref, Web of Science, Google Scholar
H. L. Kee et al. , Photochem. Photobiol. 83 , 1110 ( 2007 ) . Crossref, Web of Science, Google Scholar
M. Taniguchi et al. , New J. Chem. 32 , 947 ( 2008 ) . Crossref, Web of Science, Google Scholar
A. Kozyrev et al. , J. Org. Chem. 77 , 10260 ( 2012 ) . Crossref, Web of Science, Google Scholar
P. G. Seybold and M. Gouterman , J. Mol. Spectrosc. 31 , 1 ( 1969 ) . Crossref, Web of Science, Google Scholar
N. Kobayashi et al. , Chem. Eur. J. 9 , 5123 ( 2003 ) . Crossref, Web of Science, Google Scholar
K. Susumu et al. , J. Mater. Chem. 11 , 2262 ( 2001 ) . Crossref, Web of Science, Google Scholar
V. S.-Y. Lin , S. G. DiMagno and M. J. Therien , Science 264 , 1105 ( 1994 ) . Crossref, Web of Science, Google Scholar
V. S.-Y. Lin and M. J. Therien , Chem. Eur. J. 1 , 645 ( 1995 ) . Crossref, Web of Science, Google Scholar
P. J. Angiolillo et al. , J. Am. Chem. Soc. 117 , 12514 ( 1995 ) . Crossref, Web of Science, Google Scholar
S. M. LeCours , S. G. DiMagno and M. J. Therien , J. Am. Chem. Soc. 118 , 11854 ( 1996 ) . Crossref, Web of Science, Google Scholar
S. M. LeCours et al. , J. Am. Chem. Soc. 119 , 12578 ( 1997 ) . Crossref, Web of Science, Google Scholar
R. Kumble et al. , J. Am. Chem. Soc. 120 , 11489 ( 1998 ) . Crossref, Web of Science, Google Scholar
R. Shediac et al. , J. Am. Chem. Soc. 122 , 7017 ( 2000 ) . Crossref, Web of Science, Google Scholar
J. T. Fletcher and M. J. Therien , J. Am. Chem. Soc. 122 , 12393 ( 2000 ) . Crossref, Web of Science, Google Scholar
P. J. Angiolillo et al. , Synth. Met. 116 , 247 ( 2001 ) . Crossref, Web of Science, Google Scholar
J. T. Fletcher and M. J. Therien , Inorg. Chem. 41 , 331 ( 2002 ) . Crossref, Web of Science, Google Scholar
J. T. Fletcher and M. J. Therien , J. Am. Chem. Soc. 124 , 4298 ( 2002 ) . Crossref, Web of Science, Google Scholar
K. Susumu and M. J. Therien , J. Am. Chem. Soc. 124 , 8550 ( 2002 ) . Crossref, Web of Science, Google Scholar
I. V. Rubtsov et al. , J. Am. Chem. Soc. 125 , 2687 ( 2003 ) . Crossref, Web of Science, Google Scholar
N. P. Redmore , I. V. Rubtsov and M. J. Therien , J. Am. Chem. Soc. 125 , 8769 ( 2003 ) . Crossref, Web of Science, Google Scholar
I. V. Rubtsov et al. , J. Am. Chem. Soc. 126 , 2684 ( 2004 ) . Crossref, Web of Science, Google Scholar
P. J. Angiolillo et al. , J. Phys. Chem. B 108 , 11893 ( 2004 ) . Crossref, Web of Science, Google Scholar
K. Susumu , T. V. Duncan and M. J. Therien , J. Am. Chem. Soc. 127 , 5186 ( 2005 ) . Crossref, Web of Science, Google Scholar
K. Susumu et al. , J. Am. Chem. Soc. 128 , 8380 ( 2006 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan et al. , J. Am. Chem. Soc. 128 , 9000 ( 2006 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan , S. P. Wu and M. J. Therien , J. Am. Chem. Soc. 128 , 10423 ( 2006 ) . Crossref, Web of Science, Google Scholar
P. R. Frail et al. , Chem. Mater. 19 , 6062 ( 2007 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan , T. Ishizuka and M. J. Therien , J. Am. Chem. Soc. 129 , 9691 ( 2007 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan et al. , J. Phys. Chem. B 114 , 14696 ( 2010 ) . Crossref, Web of Science, Google Scholar
P. J. Angiolillo et al. , Chem. Commun. 49 , 9722 ( 2013 ) . Crossref, Web of Science, Google Scholar
S. M. LeCours et al. , J. Am. Chem. Soc. 118 , 1497 ( 1996 ) . Crossref, Web of Science, Google Scholar
S. Priyadarshy , M. J. Therien and D. N. Beratan , J. Am. Chem. Soc. 118 , 1504 ( 1996 ) . Crossref, Web of Science, Google Scholar
L. Karki et al. , J. Am. Chem. Soc. 120 , 2606 ( 1998 ) . Crossref, Web of Science, Google Scholar
H. T. Uyeda et al. , J. Am. Chem. Soc. 124 , 13806 ( 2002 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan et al. , J. Am. Chem. Soc. 126 , 9474 ( 2004 ) . Crossref, Web of Science, Google Scholar
T.-G. Zhang et al. , J. Am. Chem. Soc. 127 , 9710 ( 2005 ) . Crossref, Web of Science, Google Scholar
T.-G. Zhang et al. , Inorg. Chem. 45 , 9703 ( 2006 ) . Crossref, Web of Science, Google Scholar
T. Xu et al. , Nano Lett. 6 , 2387 ( 2006 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan et al. , Angew. Chem. Int. Ed. 47 , 2978 ( 2008 ) . Crossref, Web of Science, Google Scholar
S. Keinan et al. , J. Phys. Chem. A 112 , 12203 ( 2008 ) . Crossref, Web of Science, Google Scholar
M. J. Therien , Nature 458 , 716 ( 2009 ) . Crossref, Web of Science, Google Scholar
X. Hu et al. , J. Phys. Chem. C 114 , 2349 ( 2010 ) . Crossref, Web of Science, Google Scholar
G. Gonella et al. , J. Am. Chem. Soc. 132 , 9693 ( 2010 ) . Crossref, Web of Science, Google Scholar
V. Krishnan et al. , J. Am. Chem. Soc. 132 , 11083 ( 2010 ) . Crossref, Web of Science, Google Scholar
T. N. Singh-Rachford et al. , J. Am. Chem. Soc. 132 , 14203 ( 2010 ) . Crossref, Web of Science, Google Scholar
T. Ishizuka et al. , J. Am. Chem. Soc. 133 , 2884 ( 2011 ) . Crossref, Web of Science, Google Scholar
N. Jiang et al. , J. Phys. Chem. C 116 , 9724 ( 2012 ) . Crossref, Web of Science, Google Scholar
H. C. Fry et al. , J. Am. Chem. Soc. 135 , 13914 ( 2013 ) . Crossref, Web of Science, Google Scholar
P. Deria et al. , J. Am. Chem. Soc. 135 , 16220 ( 2013 ) . Crossref, Web of Science, Google Scholar
J. C. Ostrowski et al. , Adv. Mater. 15 , 1296 ( 2003 ) . Crossref, Web of Science, Google Scholar
P. Banerjee et al. , ACS Nano 4 , 1019 ( 2010 ) . Crossref, Web of Science, Google Scholar
D. Conklin et al. , Adv. Funct. Mater. 21 , 4712 ( 2011 ) . Crossref, Web of Science, Google Scholar
D. Conklin et al. , Nano Lett. 12 , 2414 ( 2012 ) . Crossref, Web of Science, Google Scholar
Z. Li et al. , Nano Lett. 12 , 2722 ( 2012 ) . Crossref, Web of Science, Google Scholar
D. Conklin et al. , ACS Nano 7 , 4479 ( 2013 ) . Crossref, Web of Science, Google Scholar
P. P. Ghoroghchian et al. , Proc. Natl. Acad. Sci. USA 102 , 2922 ( 2005 ) . Crossref, Web of Science, Google Scholar
P. P. Ghoroghchian et al. , J. Am. Chem. Soc. 127 , 15388 ( 2005 ) . Crossref, Web of Science, Google Scholar
S. P. Wu et al. , Bioconjugate Chem. 16 , 542 ( 2005 ) . Crossref, Web of Science, Google Scholar
P. P. Ghoroghchian et al. , Soft Matter 2 , 973 ( 2006 ) . Crossref, Web of Science, Google Scholar
P. P. Ghoroghchian et al. , Chem. Mater. 19 , 1309 ( 2007 ) . Crossref, Web of Science, Google Scholar
N. A. Christian et al. , Bioconjugate Chem. 18 , 31 ( 2007 ) . Crossref, Web of Science, Google Scholar
T. V. Duncan et al. , J. Am. Chem. Soc. 130 , 9773 ( 2008 ) . Crossref, Web of Science, Google Scholar
P. P. Ghoroghchian , M. J. Therien and D. A. Hammer , Wiley Interdiscip. Rev.: Nanomed. Nanobiotechnol. 1 , 156 ( 2009 ) . Crossref, Web of Science, Google Scholar
N. A. Christian et al. , Mol. Imaging Biol. 11 , 167 ( 2009 ) . Crossref, Web of Science, Google Scholar
N. P. Kamat et al. , Proc. Natl. Acad. Sci. U.S.A. 108 , 13984 ( 2011 ) . Crossref, Web of Science, Google Scholar
K. Pilgram , M. Zupan and R. Skiles , J. Heterocycl. Chem. 7 , 629 ( 1970 ) . Crossref, Web of Science, Google Scholar
K. Susumu et al. , J. Phys. Chem. A 115 , 5525 ( 2011 ) . Crossref, Web of Science, Google Scholar
D. J. Quimby and F. R. Longo , J. Am. Chem. Soc. 97 , 5111 ( 1975 ) . Crossref, Web of Science, Google Scholar
M. Velusamy et al. , Org. Lett. 7 , 1899 ( 2005 ) . Crossref, Web of Science, Google Scholar
E. Bundgaard and F. C. Krebs , Sol. Energy Mater. Sol. Cells 91 , 954 ( 2007 ) . Crossref, Web of Science, Google Scholar
J. Linnanto and J. Korppi-Tommola , J. Phys. Chem. A 105 , 3855 ( 2001 ) . Crossref, Web of Science, Google Scholar
B. A. D. Neto et al. , Eur. J. Org. Chem. 228 ( 2013 ) . Crossref, Web of Science, Google Scholar