Cyclopentene Ring Effects in Cyanine Dyes: a Handle to Fine-tune Photophysical Properties

Overview

Journal Phys Chem Chem Phys

Publisher Royal Society of Chemistry

Specialties Biophysics
Chemistry

Date 2024 Feb 2

PMID 38305348

Authors

Natalia P Neme

Thomas L C Jansen

Remco W A Havenith

Affiliations

Soon will be listed here.

Abstract

The aim of this study is to investigate the photophysical properties of a cyanine dye analogue by performing first-principles calculations based on density functional theory (DFT) and time dependent-DFT. Cationic cyanine dyes are the subject of great importance due to their versatile applications and the tunability of their photophysical properties, such as by modifying their end groups and chain length. An example of this is the vinylene shift, which is experimentally known for these molecules, and it consists of a bathochromic (red) shift of approximately 100 nm of the 0-0 vibronic transition when a vinyl group is added to the polymethine chain. Our study shows that when the saturated moiety CH of the cyclopentene ring is added to the chain, it interacts with the conjugated π-system, resulting in a smaller HOMO-LUMO gap. Here, we demonstrate the origin of this interaction and how it can be used to fine tune the absorption energies of this class of dyes.

References

Tan X, Constantin T, Sloane K, Waggoner A, Bruchez M, Armitage B . Fluoromodules Consisting of a Promiscuous RNA Aptamer and Red or Blue Fluorogenic Cyanine Dyes: Selection, Characterization, and Bioimaging. J Am Chem Soc. 2017; 139(26):9001-9009. DOI: 10.1021/jacs.7b04211. View

van Lenthe E, Baerends E . Optimized Slater-type basis sets for the elements 1-118. J Comput Chem. 2003; 24(9):1142-56. DOI: 10.1002/jcc.10255. View

Glendening E, Landis C, Weinhold F . NBO 6.0: natural bond orbital analysis program. J Comput Chem. 2013; 34(16):1429-37. DOI: 10.1002/jcc.23266. View

Neese F, Wennmohs F, Becker U, Riplinger C . The ORCA quantum chemistry program package. J Chem Phys. 2020; 152(22):224108. DOI: 10.1063/5.0004608. View

Mishra A, Behera R, Behera P, Mishra B, Behera G . Cyanines during the 1990s: A Review. Chem Rev. 2001; 100(6):1973-2012. DOI: 10.1021/cr990402t. View

Grimme S . Semiempirical hybrid density functional with perturbative second-order correlation. J Chem Phys. 2006; 124(3):034108. DOI: 10.1063/1.2148954. View

Zhekova H, Krykunov M, Autschbach J, Ziegler T . Applications of Time Dependent and Time Independent Density Functional Theory to the First π to π* Transition in Cyanine Dyes. J Chem Theory Comput. 2015; 10(8):3299-307. DOI: 10.1021/ct500292c. View

Komljenovic D, Wiessler M, Waldeck W, Ehemann V, Pipkorn R, Schrenk H . NIR-Cyanine Dye Linker: a Promising Candidate for Isochronic Fluorescence Imaging in Molecular Cancer Diagnostics and Therapy Monitoring. Theranostics. 2016; 6(1):131-41. PMC: 4679360. DOI: 10.7150/thno.11460. View

Stummer W, Stocker S, Novotny A, Heimann A, Sauer O, Kempski O . In vitro and in vivo porphyrin accumulation by C6 glioma cells after exposure to 5-aminolevulinic acid. J Photochem Photobiol B. 1998; 45(2-3):160-9. DOI: 10.1016/s1011-1344(98)00176-6. View

10.

Le Guennic B, Jacquemin D . Taking up the cyanine challenge with quantum tools. Acc Chem Res. 2015; 48(3):530-7. PMC: 4365665. DOI: 10.1021/ar500447q. View

11.

Laurent A, Adamo C, Jacquemin D . Dye chemistry with time-dependent density functional theory. Phys Chem Chem Phys. 2014; 16(28):14334-56. DOI: 10.1039/c3cp55336a. View

12.

Jacquemin D, Zhao Y, Valero R, Adamo C, Ciofini I, Truhlar D . Verdict: Time-Dependent Density Functional Theory "Not Guilty" of Large Errors for Cyanines. J Chem Theory Comput. 2015; 8(4):1255-9. DOI: 10.1021/ct200721d. View

13.

Franchini M, Philipsen P, Visscher L . The Becke fuzzy cells integration scheme in the Amsterdam density functional program suite. J Comput Chem. 2013; 34(21):1819-27. DOI: 10.1002/jcc.23323. View

14.

Wang H, Xu Y, Pang T, Chen B, Xin F, Xing M . Engineering Er-sensitized nanocrystals to enhance NIR II-responsive upconversion luminescence. Nanoscale. 2022; 14(3):962-968. DOI: 10.1039/d1nr06945d. View

15.

Higuchi K, Sato Y, Togashi N, Suzuki M, Yoshino Y, Nishizawa S . Bright and Light-Up Sensing of Benzo[]indole-oxazolopyridine Cyanine Dye for RNA and Its Application to Highly Sensitive Imaging of Nucleolar RNA in Living Cells. ACS Omega. 2022; 7(27):23744-23748. PMC: 9280936. DOI: 10.1021/acsomega.2c02408. View

16.

Send R, Valsson O, Filippi C . Electronic Excitations of Simple Cyanine Dyes: Reconciling Density Functional and Wave Function Methods. J Chem Theory Comput. 2015; 7(2):444-55. DOI: 10.1021/ct1006295. View

17.

Auzel F . Upconversion and anti-Stokes processes with f and d ions in solids. Chem Rev. 2004; 104(1):139-73. DOI: 10.1021/cr020357g. View

18.

Pascal S, Haefele A, Monnereau C, Charaf-Eddin A, Jacquemin D, Le Guennic B . Expanding the polymethine paradigm: evidence for the contribution of a bis-dipolar electronic structure. J Phys Chem A. 2014; 118(23):4038-47. DOI: 10.1021/jp501358q. View

19.

Weingarten D, LaCount M, Lagemaat J, Rumbles G, Lusk M, Shaheen S . Experimental demonstration of photon upconversion via cooperative energy pooling. Nat Commun. 2017; 8:14808. PMC: 5355946. DOI: 10.1038/ncomms14808. View

20.

Sun C, Li B, Zhao M, Wang S, Lei Z, Lu L . -Aggregates of Cyanine Dye for NIR-II Dynamic Vascular Imaging beyond 1500 nm. J Am Chem Soc. 2019; 141(49):19221-19225. DOI: 10.1021/jacs.9b10043. View