Optical Study of Solvatochromic Isocyanoaminoanthracene Dyes and 1,5-Diaminoanthracene
Abstract
:1. Introduction
2. Results and Discussion
2.1. UV–Vis Electronic Absorption Properties of 1-Amino-5-Isocyanoanthracene Derivatives
2.2. Steady-State Fluorescence Properties
2.3. Fluorescence Quantum Yield of ICAA Derivatives in Different Solvents
3. Materials and Methods
3.1. Synthesis
3.1.1 1-Amino-5-Isocyanoanthracene (ICAA) and 1,5-Diisocyanoanthracene (DIA)
3.1.2 1-N-Methylamino-5-Isocyanoanthracene (MICAA) and 1-N,N-Dimethylamino-5-Isocyanoanthracene (DIMICAA)
3.2. Fluorescence Measurements
3.3. Density Functional Theory (DFT) Calculations
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
- Bendikov, M.; Wudl, F.; Perepichka, D.F. Tetrathiafulvalenes, Oligoacenenes and Their Buckminsterfullerene Derivatives: The Brick and Mortar of Organic Electronics. Chem. Rev. 2004, 104, 4891–4946. [Google Scholar] [CrossRef] [PubMed]
- Anthony, J.E. Functionalized Acenes and Heteroacenes for Organic Electronics. Chem. Rev. 2006, 106, 5028–5048. [Google Scholar] [CrossRef] [PubMed]
- Anthony, J.E. The Larger Acenes: Versatile Organic Semiconductors. Angew. Chem. Int. Ed. 2008, 47, 452–483. [Google Scholar] [CrossRef] [PubMed]
- Chen, L.; Hernandez, Y.; Feng, X.; Müllen, K. From Nanographene and Graphene Nanoribbons to Graphene Sheets: Chemical Synthesis. Angew. Chem. Int. Ed. 2012, 51, 7640–7654. [Google Scholar] [CrossRef] [PubMed]
- Mateo-Alonso, A. Pyrene-fused pyrazaacenes: From small molecules to nanoribbons. Chem. Soc. Rev. 2014, 43, 6311–6324. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Lin, Y.-Z.; Huang, C.H.; Chang, Y.J.; Yeh, C.-W.; Chin, T.-M.; Chi, K.-M.; Chou, P.-T.; Watanabe, M.; Chow, T.J. Anthracene based organic dipolar compounds for sensitized solar cells. Tetrahedron 2014, 70, 262–269. [Google Scholar] [CrossRef]
- Nguyen, M.-H.; Nguyen, T.-N.; Do, D.-Q.; Nguyen, H.-H.; Phung, Q.-M.; Thirumalaivasan, N.; Wu, S.-P.; Dinh, T.-H. A highly selective fluorescent anthracene-based chemosensor for imaging Zn2+ in living cells and zebrafish. Inorg. Chem. Commun. 2020, 115, 107882. [Google Scholar] [CrossRef]
- Gómez, P.; Cerdá, J.; Más-Montoya, M.; Georgakopoulos, S.; da Silva, I.; García, A.; Ortí, E.; Aragó, J.; Curiel, D. Effect of molecular geometry and extended conjugation on the performance of hydrogen-bonded semiconductors in organic thin-film field-effect transistors. J. Mater. Chem. C 2021, 9, 10819–10829. [Google Scholar] [CrossRef]
- Matsumoto, H.; Nishimura, Y.; Arai, T. Excited-state intermolecular proton transfer dependent on the substitution pattern of anthracene–diurea compounds involved in fluorescent ON1–OFF–ON2 response by the addition of acetate ions. Org. Biomol. Chem. 2017, 15, 6575–6583. [Google Scholar] [CrossRef]
- Black, H.T.; Lin, H.; Bélanger-Gariépy, F.; Perepichka, D.F. Supramolecular control of organic p/n-heterojunctions by complementary hydrogen bonding. Faraday Discuss. 2014, 174, 297–312. [Google Scholar] [CrossRef]
- Głowacki, E.D.; Irimia-Vladu, M.; Bauer, S.; Sariciftci, N.S. Hydrogen-bonds in molecular solids–from biological systems to organic electronics. J. Mater. Chem. B 2013, 1, 3742–3753. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Irimia-Vladu, M.; Kanbur, Y.; Camaioni, F.; Coppola, M.E.; Yumusak, C.; Irimia, C.V.; Vlad, A.; Operamolla, A.; Farinola, G.M.; Suranna, G.P.; et al. Stability of Selected Hydrogen Bonded Semiconductors in Organic Electronic Devices. Chem. Mater. 2019, 31, 6315–6346. [Google Scholar] [CrossRef] [PubMed]
- Gómez, P.; Georgakopoulos, S.; Más-Montoya, M.; Cerdá, J.; Pérez, J.; Ortí, E.; Aragó, J.; Curiel, D. Improving the Robustness of Organic Semiconductors through Hydrogen Bonding. ACS Appl. Mater. Interfaces 2021, 13, 8620–8630. [Google Scholar] [CrossRef] [PubMed]
- Feng, C.; Zhou, S.; Wang, D.; Zhao, Y.; Liu, S.; Li, Z.; Braunstein, P. Cooperativity in Highly Active Ethylene Dimerization by Dinuclear Nickel Complexes Bearing a Bifunctional PN Ligand. Organometallics 2021, 40, 184–193. [Google Scholar] [CrossRef]
- Más-Montoya, M.; Gómez, P.; Curiel, D.; Da Silva, I.; Wang, J.; Janssen, R.A.J. A Self-Assembled Small-Molecule-Based Hole-Transporting Material for Inverted Perovskite Solar Cells. Chem. A Eur. J. 2020, 26, 10276–10282. [Google Scholar] [CrossRef]
- Wright, T.; Tomkovic, T.; Hatzikiriakos, S.G.; Wolf, M.O. Photoactivated Healable Vitrimeric Copolymers. Macromolecules 2018, 52, 36–42. [Google Scholar] [CrossRef]
- Guo, Z.; Sun, P.; Zhang, X.; Lin, J.; Shi, T.; Liu, S.; Sun, A.; Li, Z. Amorphous Porous Organic Polymers Based on Schiff-Base Chemistry for Highly Efficient Iodine Capture. Chem. Asian J. 2018, 13, 2046–2053. [Google Scholar] [CrossRef]
- Shi, T.; Zheng, Q.-D.; Zuo, W.-W.; Liu, S.-F.; Li, Z.-B. Bimetallic aluminum complexes supported by bis(salicylaldimine) ligand: Synthesis, characterization and ring-opening polymerization of lactide. Chin. J. Polym. Sci. 2017, 36, 149–156. [Google Scholar] [CrossRef]
- Li, X.-Z.; Zhou, L.-P.; Yan, L.-L.; Yuan, D.-Q.; Lin, C.-S.; Sun, Q.-F. Evolution of Luminescent Supramolecular Lanthanide M2nL3n Complexes from Helicates and Tetrahedra to Cubes. J. Am. Chem. Soc. 2017, 139, 8237–8244. [Google Scholar] [CrossRef]
- Kuster, S.; Geiger, T. Coupled π-conjugated chromophores: Squaraine dye dimers as two connected pendulums. Dye. Pigment. 2015, 113, 110–116. [Google Scholar] [CrossRef]
- Rácz, D.; Nagy, M.; Mándi, A.; Zsuga, M.; Kéki, S. Solvatochromic properties of a new isocyanonaphthalene based fluorophore. J. Photochem. Photobiol. A Chem. 2013, 270, 19–27. [Google Scholar] [CrossRef] [Green Version]
- Lakowicz, J.R. Principles of Fluorescence Spectroscopy; Springer: New York, NY, USA, 2006. [Google Scholar]
- Marini, A.; Muñoz-Losa, A.; Biancardi, A.; Mennucci, B. What is Solvatochromism? J. Phys. Chem. B 2010, 114, 17128–17135. [Google Scholar] [CrossRef] [PubMed]
- Nagy, M.; Rácz, D.; Lázár, L.; Purgel, M.; Ditrói, T.; Zsuga, M.; Kéki, S. Solvatochromic Study of Highly Fluorescent Alkylated Isocyanonaphthalenes, Their π-Stacking, Hydrogen-Bonding Complexation, and Quenching with Pyridine. Chemphyschem 2014, 15, 3614–3625. [Google Scholar] [CrossRef] [PubMed]
- Nagy, M.; Rácz, D.; Nagy, Z.L.; Nagy, T.; Fehér, P.P.; Purgel, M.; Zsuga, M.; Kéki, S. An acrylated isocyanonaphthalene based solvatochromic click reagent: Optical and biolabeling properties and quantum chemical modeling. Dye. Pigm. 2016, 133, 445–457. [Google Scholar] [CrossRef] [Green Version]
- Nagy, M.; Rácz, D.; Nagy, Z.L.; Fehér, P.P.; Kalmár, J.; Fábián, I.; Kiss, A.; Zsuga, M.; Kéki, S. Solvatochromic isocyanonaphthalene dyes as ligands for silver(I) complexes, their applicability in silver(I) detection and background reduction in biolabelling. Sens. Actuators B Chem. 2018, 255, 2555–2567. [Google Scholar] [CrossRef] [Green Version]
- Nagy, M.; Kéki, S.; Rácz, D.; Mathur, J.; Vereb, G.; Garda, T.; M-Hamvas, M.; Chaumont, F.; Bóka, K.; Böddi, B.; et al. Novel fluorochromes label tonoplast in living plant cells and reveal changes in vacuolar organization after treatment with protein phosphatase inhibitors. Protoplasma 2017, 255, 829–839. [Google Scholar] [CrossRef] [Green Version]
- Nagy, Z.; Nagy, M.; Kiss, A.; Rácz, D.; Barna, B.; Konczol, P.; Bankó, C.; Bacsó, Z.; Kéki, S.; Bánfalvi, G.; et al. MICAN, a new fluorophore for vital and non-vital staining of human cells. Toxicol. Vitr. 2018, 48, 137–145. [Google Scholar] [CrossRef]
- Nagy, M.; Kovács, S.L.; Nagy, T.; Rácz, D.; Zsuga, M.; Kéki, S. Isocyanonaphthalenes as extremely low molecular weight, selective, ratiometric fluorescent probes for Mercury(II). Talanta 2019, 201, 165–173. [Google Scholar] [CrossRef]
- Nagy, M.; Szemán-Nagy, G.; Kiss, A.; Nagy, Z.L.; Tálas, L.; Rácz, D.; Majoros, L.; Tóth, Z.; Szigeti, Z.M.; Pócsi, I.; et al. Antifungal Activity of an Original Amino-Isocyanonaphthalene (ICAN) Compound Family: Promising Broad Spectrum Antifungals. Molecules 2020, 25, 903. [Google Scholar] [CrossRef] [Green Version]
- Nagy, M.; Rácz, D.; Nagy, Z.L.; Fehér, P.P.; Kovács, S.L.; Bankó, C.; Bacsó, Z.; Kiss, A.; Zsuga, M.; Kéki, S. Amino-isocyanoacridines: Novel, Tunable Solvatochromic Fluorophores as Physiological pH Probes. Sci. Rep. 2019, 9, 8250. [Google Scholar] [CrossRef]
- Bankó, C.; Nagy, Z.L.; Nagy, M.; Szemán-Nagy, G.G.; Rebenku, I.; Imre, L.; Tiba, A.; Hajdu, A.; Szöllősi, J.; Kéki, S.; et al. Isocyanide Substitution in Acridine Orange Shifts DNA Damage-Mediated Phototoxicity to Permeabilization of the Lysosomal Membrane in Cancer Cells. Cancers 2021, 13, 5652. [Google Scholar] [CrossRef] [PubMed]
- Berlman, I.B. Handbook of Fluorescence Spectra of Aromatic Molecules; Academic Press: New York, NY, USA, 1971. [Google Scholar]
- Poteau, X.; Brown, A.I.; Brown, R.G.; Holmes, C.; Matthew, D. Fluorescence switching in 4-amino-1,8-naphthalimides: “on–off–on” operation controlled by solvent and cations. Dye. Pigment. 2000, 47, 91–105. [Google Scholar] [CrossRef]
- Staneva, D.; Vasileva-Tonkova, E.; Grabchev, I. Chemical modification of cotton fabric with 1,8-naphthalimide for use as heterogeneous sensor and antibacterial textile. J. Photochem. Photobiol. A Chem. 2019, 382, 111924. [Google Scholar] [CrossRef]
- Reichardt, C. Solvatochromic Dyes as Solvent Polarity Indicators. Chem. Rev. 1994, 94, 2319–2358. [Google Scholar] [CrossRef]
- Lippert, E. Dipolmoment und Elektronenstruktur von angeregten Molekülen. Z. Für Nat. A 1955, 10, 541–545. [Google Scholar] [CrossRef] [Green Version]
- Mataga, N.; Kaifu, Y.; Koizumi, M. The Solvent Effect on Fluorescence Spectrum, Change of Solute-Solvent Interaction during the Lifetime of Excited Solute Molecule. Bull. Chem. Soc. Jpn. 1955, 28, 690–691. [Google Scholar] [CrossRef] [Green Version]
- Suppan, P. Excited-state dipole moments from absorption/fluorescence solvatochromic ratios. Chem. Phys. Lett. 1983, 94, 272–275. [Google Scholar] [CrossRef]
- Menges, F. “Spectragryph—Optical Spectroscopy Software”, Version 1.2.15. 2020. Available online: http://www.effemm2.de/spectragryph/ (accessed on 30 December 2021).
- Kovács, S.L.; Nagy, M.; Fehér, P.P.; Zsuga, M.; Kéki, S. Effect of the Substitution Position on the Electronic and Solvatochromic Properties of Isocyanoaminonaphthalene (ICAN) Fluorophores. Molecules 2019, 24, 2434. [Google Scholar] [CrossRef] [Green Version]
- Kovács, E.; Faigl, F.; Mucsi, Z. Regio- and Diastereoselective Synthesis of 2-Arylazetidines: Quantum Chemical Explanation of Baldwin’s Rules for the Ring-Formation Reactions of Oxiranes. J. Org. Chem. 2020, 85, 11226–11239. [Google Scholar] [CrossRef]
- Kovács, E.; Cseri, L.; Jancsó, A.; Terényi, F.; Fülöp, A.; Rózsa, B.; Galbács, G.; Mucsi, Z. Synthesis and Fluorescence Mechanism of the Aminoimidazolone Analogues of the Green Fluorescent Protein: Towards Advanced Dyes with Enhanced Stokes Shift, Quantum Yield and Two-Photon Absorption. Eur. J. Org. Chem. 2021, 2021, 5649–5660. [Google Scholar] [CrossRef]
- Zhao, Y.; Truhlar, D.G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215–241. [Google Scholar] [CrossRef] [Green Version]
- Schäfer, A.; Huber, C.; Ahlrichs, R. Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J. Chem. Phys. 1994, 100, 5829–5835. [Google Scholar] [CrossRef]
- Miertuš, S.; Scrocco, E.; Tomasi, J. Electrostatic interaction of a solute with a continuum. A direct utilization of AB initio molecular potentials for the prevision of solvent effects. Chem. Phys. 1981, 55, 117–129. [Google Scholar] [CrossRef]
- Caricato, M.; Mennuccia, B.; Tomasi, J.; Ingrosso, F.; Cammi, R.; Corni, S.; Scalmani, G. Formation and relaxation of excited states in solution: A new time dependent polarizable continuum model based on time dependent density functional theory. J. Chem. Phys. 2006, 124, 124520. [Google Scholar] [CrossRef]
Solvent (εr) | DAA | ICAA | MICAA | DIMICAA | ||||
---|---|---|---|---|---|---|---|---|
λAbs (nm) | ε ×10−3 (M−1cm−1) | λAbs (nm) | ε ×10−3 (M−1cm−1) | λAbs (nm) | ε ×10−3 (M−1cm−1) | λAbs (nm) | ε ×10−3 (M−1cm−1) | |
n-Hexane (1.89) | 403 | 4.4 | 412 | 3.9 | 432 | 3.9 | 397 | 4.9 |
Toluene (2.38) | 409 | 5.4 | 420 | 3.8 | 433 | 4.1 | 401 | 4.8 |
DCM (8.93) | 407 | 4.7 | 417 | 3.9 | 431 | 4.0 | 404 | 4.8 |
2-propanol (17.9) | 403 | 4.6 | 426 | 3.6 | 434 | 3.9 | 403 | 4.9 |
THF (7.58) | 416 | 5.0 | 435 | 3.1 | 445 | 3.7 | 404 | 4.8 |
Chloroform (4.81) | 404 | 4.6 | 414 | 3.8 | 431 | 3.9 | 404 | 4.8 |
EtOAc (6.02) | 411 | 4.8 | 425 | 3.2 | 437 | 4.0 | 400 | 4.9 |
Dioxane (2.25) | 415 | 5.2 | 426 | 3.7 | 438 | 4.1 | 402 | 5.1 |
Acetone (20.7) | 415 | 4.8 | 430 | 3.2 | 441 | 3.7 | 400 | 4.6 |
Methanol (32.7) | 406 | 4.4 | 426 | 3.3 | 427 | 3.7 | 398 | 4.9 |
Pyridine (12.4) | 423 | 5.7 | 426 | 3.1 | 451 | 4.0 | 407 | 4.8 |
Acetonitrile (37.5) | 410 | 5.0 | 422 | 3.7 | 434 | 4.0 | 403 | 4.9 |
DMF (36.7) | 421 | 5.4 | 442 | 3.1 | 449 | 3.9 | 404 | 4.9 |
DMSO (46.7) | 426 | 5.3 | 444 | 3.4 | 451 | 4.0 | 409 | 4.9 |
Water (80.1) | 395 | 4.6 | 410 | 3.6 | 415 | 3.4 | 400 | 3.9 |
Hexane | Dioxane | Water | |||||
---|---|---|---|---|---|---|---|
d (N-N) | µ | d (N-N) | µ | d (N-N) | µ | ||
S0 (Ground State) | Angstrom | Debye | Angstrom | Debye | Angstrom | Debye | |
DAA | 7.492 | 2.03 | 7.493 | 2.07 | 7.501 | 2.49 | |
ICAA | 7.473 | 6.05 | 7.474 | 6.19 | 7.478 | 7.29 | |
MICAA | 7.479 | 5.55 | 7.480 | 5.67 | 7.488 | 6.50 | |
DIMICAA | 7.476 | 5.52 | 7.477 | 5.64 | 7.482 | 6.50 | |
DIA | 7.446 | 0.00 | 7.447 | 0.00 | 7.452 | 0.00 | |
S1opt (Excited State) | Angstrom | Debye | Angstrom | Debye | Angstrom | Debye | |
DAA | 7.502 | 1.64 | 7.504 | 1.66 | 7.514 | 1.84 | |
ICAA | 7.462 | 12.15 | 7.463 | 12.45 | 7.472 | 14.64 | |
MICAA | 7.541 | 12.98 | 7.543 | 13.32 | 7.554 | 15.81 | |
DIMICAA | 7.510 | 13.02 | 7.511 | 13.36 | 7.519 | 15.78 | |
DIA | 7.445 | 0.00 | 7.446 | 0.00 | 7.451 | 0.00 |
1,5-DAA | 1,5-ICAA | 1,5-MICAA | 1,5-DIMICAA | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
Solvent | λEm (nm) | √f (%) | (cm−1) | λEm (nm) | √f (%) | (cm−1) | λEm (nm) | √f (%) | (cm−1) | λEm (nm) | √f (%) | (cm−1) |
n-Hexane | 475 | 21 | 3761 | 527 | 13 | 5297 | 521 | 12 | 3954 | 521 | 14 | 5995 |
Toluene | 485 | 38 | 3831 | 532 | 14 | 5013 | 536 | 11 | 4438 | 550 | 11 | 6756 |
DCM | 490 | 40 | 4162 | 555 | 6.7 | 5963 | 562 | 5.9 | 5408 | 567 | 5.9 | 7116 |
2-propanol | 519 | 23 | 5546 | 572 | 0.4 | 5992 | 571 | 1.0 | 5528 | 571 | 1.7 | 7301 |
THF | 493 | 34 | 3754 | 566 | 2.9 | 5321 | 566 | 3.7 | 4804 | 567 | 4.5 | 7116 |
Chloroform | 490 | 12 | 4717 | 551 | 7.8 | 6006 | 557 | 7.0 | 5249 | 562 | 9.7 | 6959 |
EtOAc | 491 | 32 | 3964 | 563 | 3.4 | 5767 | 564 | 3.4 | 5153 | 568 | 3.8 | 7394 |
Dioxane | 492 | 53 | 3771 | 557 | 6.6 | 5521 | 558 | 7.5 | 4910 | 563 | 9.0 | 7114 |
Acetone | 497 | 25 | 3976 | 572 | 1.1 | 5773 | 571 | 1.3 | 5163 | 573 | 1.6 | 7548 |
Methanol | 516 | 17 | 5251 | 571 | 0.3 | 5961 | 571 | 0.5 | 5906 | 571 | 0.8 | 7612 |
Pyridine | 508 | 22 | 3956 | 571 | 1.3 | 5961 | 571 | 1.5 | 4660 | 570 | 3.7 | 7026 |
Acetonitrile | 500 | 28 | 4390 | 571 | 0.9 | 6184 | 571 | 0.8 | 5528 | 575 | 0.9 | 7423 |
DMF | 506 | 37 | 3990 | 576 | 0.4 | 5263 | 572 | 0.8 | 4820 | 578 | 0.9 | 7451 |
DMSO | 511 | 45 | 3905 | 576 | 0.3 | 5160 | 573 | 0.9 | 4720 | 577 | 1.0 | 7119 |
Water | 546 | 3.1 | 7001 | 530 | 0.1 | - | 559 | 0.2 | 6207 | 567 | 0.2 | 7363 |
(μE − μG)DFT (D) | (μE − μG)LM (D) | |||
---|---|---|---|---|
Hexane | Dioxane | Water | ||
DAA | −0.39 | −0.41 | −0.65 | 2.22 |
ICAA | 6.10 | 6.26 | 7.35 | 3.07 |
MICAA | 7.31 | 7.77 | 9.31 | 3.98 |
DIMICAA | 7.49 | 7.72 | 9.28 | 3.88 |
DIA | 0.00 | 0.00 | 0.00 | 0.00 |
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. |
© 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Nagy, M.; Fiser, B.; Szőri, M.; Vanyorek, L.; Viskolcz, B. Optical Study of Solvatochromic Isocyanoaminoanthracene Dyes and 1,5-Diaminoanthracene. Int. J. Mol. Sci. 2022, 23, 1315. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23031315
Nagy M, Fiser B, Szőri M, Vanyorek L, Viskolcz B. Optical Study of Solvatochromic Isocyanoaminoanthracene Dyes and 1,5-Diaminoanthracene. International Journal of Molecular Sciences. 2022; 23(3):1315. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23031315
Chicago/Turabian StyleNagy, Miklós, Béla Fiser, Milán Szőri, László Vanyorek, and Béla Viskolcz. 2022. "Optical Study of Solvatochromic Isocyanoaminoanthracene Dyes and 1,5-Diaminoanthracene" International Journal of Molecular Sciences 23, no. 3: 1315. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms23031315