Twisted 8-Acyl-1-dialkyl-amino-naphthalenes Emit from a Planar Intramolecular Charge Transfer Excited State
Abstract
:1. Introduction
2. Materials and Methods
2.1. 1-(Methylamino)naphthalene (11)
2.2. 1-(Dimethylamino)naphthalene (12)
2.3. 1-Acetyl-(8-dimethylamino)naphthalene (3)
2.4. 1-Pivaloyl-(8-dimethylamino)naphthalene (4)
2.5. 3-(Methyl(naphthalen-1-yl)amino)propanoic Acid (14)
2.6. 1-Methyl-2,3-dihydronaphtho[1,8-bc]azepin-4(1H)-one (5)
2.7. 1H-naphtho[1,8-de][1,2,3]triazine (16)
2.8. 1-Amino-8-bromonaphthalene (17)
2.9. 1-(Dimethylamino)-8-bromonaphthalene (18)
2.10. 1-Cyano-8-(dimethylamino)naphthalene (6)
3. Results
3.1. Photophysical Studies
3.1.1. Absorption
3.1.2. Fluorescence
3.1.3. Solvato-Chromism
3.1.4. Fluorescence Quenching by Protic Solvents
3.2. Computational Studies
4. Discussion
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Weber, G.; Farris, F.J. Synthesis and Spectral Properties of a Hydrophobic Fluorescent Probe: 6-Propionyl-2-(Dimethylamino) Naphthalene. Biochemistry 1979, 18, 3075–3078. [Google Scholar] [CrossRef] [PubMed]
- Balter, A.; Nowak, W.; Pawekiewicz, W.; Kowalczyk, A. Some Remarks on the Interpretation of the Spectral Properties of Prodan. Chem. Phys. Lett. 1988, 143, 565–570. [Google Scholar] [CrossRef]
- Catalán, J.; Perez, P.; Laynez, J.; Blanco, F.G. Analysis of the Solvent Effect on the Photophysics Properties of 6-Propionyl-2-(Dimethylamino) Naphthalene (PRODAN). J. Fluoresc. 1991, 1, 215–223. [Google Scholar] [CrossRef] [PubMed]
- Kawski, A. Ground-and Excited-State Dipole Moments of 6-Propionyl-2-(Dimethylamino) Naphthalene Determined from Solvatochromic Shifts. Z. Für Naturforschung A 1999, 54, 379–381. [Google Scholar] [CrossRef]
- Samanta, A.; Fessenden, R.W. Excited State Dipole Moment of PRODAN as Determined from Transient Dielectric Loss Measurements. J. Phys. Chem. A 2000, 104, 8972–8975. [Google Scholar] [CrossRef]
- Benedetti, E.; Kocsis, L.S.; Brummond, K.M. Synthesis and Photophysical Properties of a Series of Cyclopenta [b] Naphthalene Solvatochromic Fluorophores. J. Am. Chem. Soc. 2012, 134, 12418–12421. [Google Scholar] [CrossRef] [PubMed]
- Jockusch, S.; Zheng, Q.; He, G.S.; Pudavar, H.E.; Yee, D.J.; Balsanek, V.; Halim, M.; Sames, D.; Prasad, P.N.; Turro, N.J. Two-Photon Excitation of Fluorogenic Probes for Redox Metabolism: Dramatic Enhancement of Optical Contrast Ratio by Two-Photon Excitation. J. Phys. Chem. C 2007, 111, 8872–8877. [Google Scholar] [CrossRef]
- Brummond, K.M.; Kocsis, L.S. Intramolecular Didehydro-Diels–Alder Reaction and Its Impact on the Structure–Function Properties of Environmentally Sensitive Fluorophores. Acc. Chem. Res. 2015, 48, 2320–2329. [Google Scholar] [CrossRef]
- Grabowski, Z.R.; Rotkiewicz, K.; Rettig, W. Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures. Chem. Rev. 2003, 103, 3899–4031. [Google Scholar] [CrossRef]
- Wang, C.; Chi, W.; Qiao, Q.; Tan, D.; Xu, Z.; Liu, X. Twisted Intramolecular Charge Transfer (TICT) and Twists beyond TICT: From Mechanisms to Rational Designs of Bright and Sensitive Fluorophores. Chem. Soc. Rev. 2021, 50, 12656–12678. [Google Scholar] [CrossRef]
- Chen, C.; Fang, C. Fluorescence Modulation by Amines: Mechanistic Insights into Twisted Intramolecular Charge Transfer (TICT) and Beyond. Chemosensors 2023, 11, 87. [Google Scholar] [CrossRef]
- Kochman, M.A.; Durbeej, B. Simulating the Nonadiabatic Relaxation Dynamics of 4-(N, N-Dimethylamino) Benzonitrile (DMABN) in Polar Solution. J. Phys. Chem. A 2020, 124, 2193–2206. [Google Scholar] [CrossRef] [PubMed]
- Okada, T.; Uesugi, M.; Köhler, G.; Rechthaler, K.; Rotkiewicz, K.; Rettig, W.; Grabner, G. Time-Resolved Spectroscopy of DMABN and Its Cage Derivatives 6-Cyanobenzquinuclidine (CBQ) and Benzquinuclidine (BQ). Chem. Phys. 1999, 241, 327–337. [Google Scholar] [CrossRef]
- Köhler, G.; Rechthaler, K.; Grabner, G.; Luboradzki, R.; Suwińska, K.; Rotkiewicz, K. Structure of Cage Amines as Models for Twisted Intramolecular Charge-Transfer States. J. Phys. Chem. A 1997, 101, 8518–8525. [Google Scholar] [CrossRef]
- Wermuth, G.; Rettig, W. The Interaction of Close-Lying Excited States: Solvent Influence on Fluorescence Rate and Polarization in Substituted Indolines. J. Phys. Chem. 1984, 88, 2729–2735. [Google Scholar] [CrossRef]
- Rotkiewicz, K.; Rubaszewska, W. Intramolecular Charge Transfer State and Unusual Fluorescence from an Upper Excited Singlet of a Nonplanar Derivative of P-Cyano-N, N-Dimethylaniline. J. Lumin. 1982, 27, 221–230. [Google Scholar] [CrossRef]
- Anderson, R.S.; Nagirimadugu, N.V.; Abelt, C.J. Fluorescence Quenching of Carbonyl-Twisted 5-Acyl-1-Dimethylaminonaphthalenes by Alcohols. ACS Omega 2019, 4, 14067–14073. [Google Scholar] [CrossRef]
- Chen, T.; Lee, S.W.; Abelt, C.J. 1,5-Prodan Emits from a Planar Intramolecular Charge-Transfer Excited State. ACS Omega 2018, 3, 4816–4823. [Google Scholar] [CrossRef]
- Davis, B.N.; Abelt, C.J. Synthesis and Photophysical Properties of Models for Twisted PRODAN and Dimethylaminonaphthonitrile. J. Phys. Chem. A 2005, 109, 1295–1298. [Google Scholar] [CrossRef]
- Everett, R.K.; Nguyen, H.A.A.; Abelt, C.J. Does PRODAN Possess an O-TICT Excited State? Synthesis and Properties of Two Constrained Derivatives. J. Phys. Chem. A 2010, 114, 4946–4950. [Google Scholar] [CrossRef]
- Lobo, B.C.; Abelt, C.J. Does PRODAN Possess a Planar or Twisted Charge-Transfer Excited State? Photophysical Properties of Two PRODAN Derivatives. J. Phys. Chem. A 2003, 107, 10938–10943. [Google Scholar] [CrossRef]
- Kiefl, C. Correlated Rotations and Unusual Fluorescence Properties of peri-Substituted, Axially Chiral Naphthyl Ketones. Eur. J. Org. Chem. 2000, 2000, 3279–3286. [Google Scholar] [CrossRef]
- Gallucci, J.C.; Hart, D.J.; Young, D.G.J. Nucleophile–Electrophile Interactions in 1,8-Disubstituted Naphthalenes: Structures of Three 1-Naphthaldehydes and a 1-Naphthyl Methyl Ketone. Acta Crystallogr. B 1998, 54, 73–81. [Google Scholar] [CrossRef]
- Schweizer, W.B.; Procter, G.; Kaftory, M.; Dunitz, J.D. Structural Studies of 1,8-Disubstituted Naphthalenes as Probes for nucleophile-electrophile interactions. Helv. Chim. Acta 1978, 61, 2783–2808. [Google Scholar] [CrossRef]
- Bulgarevich, S.B.; Ivanova, N.A.; Movshovich, D.Y.; Mannschreck, A.; Kiefl, C. Conformational Investigation of 1,8-Disubstituted Naphthalenes as Solutes by Kerr Effect and Dipole Moment Methods. J. Mol. Struct. 1994, 326, 17–24. [Google Scholar] [CrossRef]
- Hodgson, D.R.W.; Kirby, A.J.; Feeder, N. The Case of the Missing Acetylene. The Mechanism of an Intramolecular SN(V) Reaction and a New Route to 1-Methylbenzo[de]Quinolines. J. Chem. Soc. Perkin 1 1999, 1, 949–954. [Google Scholar] [CrossRef]
- Clayden, J.; McCarthy, C.; Helliwell, M. Bonded Peri-Interactions Govern the Rate of Racemisation of Atropisomeric 8-Substituted 1-Naphthamides. Chem. Commun. 1999, 20, 2059–2060. [Google Scholar] [CrossRef]
- Noyes, W.A. n-BUTYL NITRITE. Org. Synth. 1936, 16, 7. [Google Scholar] [CrossRef]
- Vogel, A.I. A Text-Book of Practical Organic Chemistry Including Qualitative Organic Analysis, 3rd ed.; Longmans: London, UK, 1974; ISBN 978-0-582-44245-0. [Google Scholar]
- Lakowicz, J.R. Principles of Fluorescence Spectroscopy; Springer: Boston, MA, USA, 1999; ISBN 978-1-4757-3063-0. [Google Scholar]
- Frisch, M.M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb, M.A.; Cheeseman, J.R.; Scalmani, G.; Barone, V.; Petersson, G.A.; Nakatsuji, H.; et al. Gaussian 16, Version 1.1; Gaussian, Inc.: Wallingford, CT, USA, 2016. [Google Scholar]
- Kirby, A.J.; Percy, J.M. Synthesis of 8-Substituted 1-Naphthylamine Derivatives. Exceptional Reactivity of the Substituents. Tetrahedron 1988, 44, 6903–6910. [Google Scholar] [CrossRef]
- Kiefl, C.; Mannschreck, A. 1,8-Disubstituted Naphthalenes by Directed Metalation and Subsequent Lithium-Manganese Exchange, Including Copper Catalysis. Synthesis 1995, 1995, 1033–1037. [Google Scholar] [CrossRef]
- Lum, K.; Zielinski, S.M.; Abelt, C.J. Dansyl Emits from a PICT Excited State. J. Phys. Chem. A 2021, 125, 1229–1233. [Google Scholar] [CrossRef] [PubMed]
- Reichardt, C.; Welton, T. Solvents and Solvent Effects in Organic Chemistry; Wiley-VCH Verlag GmbH: Weinheim, Germany, 2011. [Google Scholar]
- Wang, C.; Qiao, Q.; Chi, W.; Chen, J.; Liu, W.; Tan, D.; McKechnie, S.; Lyu, D.; Jiang, X.; Zhou, W.; et al. Quantitative Design of Bright Fluorophores and AIEgens by the Accurate Prediction of Twisted Intramolecular Charge Transfer (TICT). Angew. Chem. Int. Ed. 2020, 59, 10160–10172. [Google Scholar] [CrossRef] [PubMed]
3 | 4 | 5 | 6 | |||||
---|---|---|---|---|---|---|---|---|
Φf | λem | Φf | λem | Φf | λem | Φf | λem | |
Solvent a | ×10−2 | (nm) | ×10−2 | (nm) | ×10−2 | (nm) | ×10−2 | (nm) |
Cyc | 6.8 | 502 | 1.1 | 487 | 21.5 | 500 | 55.5 | 464 |
Tol | 7.9 | 538 | 3.0 | 520 | 37.0 | 539 | 43.2 | 491 |
PhCl | 7.3 | 558 | 3.8 | 532 | 23.6 | 559 | 54.4 | 480 |
CH2Cl2 | 4.5 | 583 | 3.2 | 554 | 16.5 | 583 | 45.8 | 508 |
EtOAc | 4.0 | 560 | 1.9 | 535 | 6.3 | 566 | 24.5 | 508 |
Et2O | 1.4 | 566 | 0.6 | 531 | 9.9 | 566 | 36.6 | 496 |
Me2CO | 2.0 | 585 | 1.4 | 556 | 8.8 | 583 | 22.3 | 522 |
MeCN | 1.5 | 603 | 1.3 | 567 | 5.6 | 598 | 22.5 | 529 |
DMSO | 1.5 | 612 | 1.6 | 576 | 4.7 | 607 | 18.7 | 542 |
iPrOH | 0.1 | 636 | - b | - b | 0.6 | 637 | 28.8 | 524 |
d1 | d2 | d3 | d4 | |d3-d4| | C=O a | C-N | QO a | QN | |||
---|---|---|---|---|---|---|---|---|---|---|---|
State | Solvent | (Degrees) | (Å) | (Mulliken) | |||||||
3 | S1 | MeCN | 19 | 20 | 31 | 24 | 7 | 1.26 | 1.37 | −0.56 | −0.01 |
Tol | 21 | 23 | 30 | 24 | 7 | 1.26 | 1.37 | −0.50 | −0.01 | ||
S0 | MeCN | 65 | 71 | 85 | 37 | 48 | 1.22 | 1.43 | −0.51 | −0.13 | |
Tol | 64 | 70 | 82 | 34 | 47 | 1.22 | 1.43 | −0.46 | −0.14 | ||
4 | S1 | MeCN | 34 | 45 | 30 | 20 | 10 | 1.26 | 1.37 | −0.52 | −0.04 |
Tol | 35 | 46 | 30 | 20 | 9 | 1.26 | 1.37 | −0.48 | −0.04 | ||
S0 | MeCN | 73 | 84 | 81 | 30 | 51 | 1.22 | 1.43 | −0.49 | −0.11 | |
Tol | 73 | 84 | 80 | 29 | 50 | 1.22 | 1.43 | −0.44 | −0.12 | ||
5 | S1 | MeCN | 14 | 25 | −25 | −22 | 3 | 1.26 | 1.36 | −0.58 | 0.14 |
Tol | 13 | 23 | −25 | −23 | 2 | 1.26 | 1.36 | −0.53 | 0.14 | ||
S0 | MeCN | 42 | 51 | −48 | −10 | 38 | 1.22 | 1.40 | −0.52 | −0.02 | |
Tol | 40 | 49 | −48 | −11 | 37 | 1.22 | 1.40 | −0.47 | 0.00 | ||
6 | S1 | MeCN | - | - | 47 | 33 | 14 | 1.17 | 1.38 | −0.34 | 0.02 |
Tol | - | - | 84 | 96 | 12 | 1.17 | 1.44 | −0.28 | 0.12 | ||
S0 | MeCN | - | - | 78 | 30 | 48 | 1.16 | 1.42 | −0.35 | −0.13 | |
Tol | - | - | 77 | 30 | 47 | 1.15 | 1.41 | −0.3 | −0.11 |
3 | 4 | 5 | 6 | |||||
---|---|---|---|---|---|---|---|---|
toluene | em | abs | em | abs | em | abs | em | abs |
λmax (nm) | 589 | 333 | 567 | 329 | 574 | 405 | 609 | 396 |
dipole moment (D) | 3.9 | 3.6 | 2.9 | 2.9 | 4.2 | 4.1 | 5.2 | 4.9 |
Stokes shift ×103 (cm−1) | 13.1 | 12.8 | 7.3 | 8.8 | ||||
acetonitrile | ||||||||
λmax (nm) | 633 | 332 | 597 | 329 | 614 | 414 | 545 | 396 |
dipole moment (D) | 4.9 | 4.4 | 3.7 | 3.7 | 5.1 | 4.9 | 4.9 | 5.9 |
Stokes shift ×103 (cm−1) | 14 | 14 | 7.9 | 6.9 |
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |
© 2024 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
Abelt, C.; Sweigart, K. Twisted 8-Acyl-1-dialkyl-amino-naphthalenes Emit from a Planar Intramolecular Charge Transfer Excited State. Photochem 2024, 4, 1-13. https://doi.org/10.3390/photochem4010001
Abelt C, Sweigart K. Twisted 8-Acyl-1-dialkyl-amino-naphthalenes Emit from a Planar Intramolecular Charge Transfer Excited State. Photochem. 2024; 4(1):1-13. https://doi.org/10.3390/photochem4010001
Chicago/Turabian StyleAbelt, Christopher, and Kirsten Sweigart. 2024. "Twisted 8-Acyl-1-dialkyl-amino-naphthalenes Emit from a Planar Intramolecular Charge Transfer Excited State" Photochem 4, no. 1: 1-13. https://doi.org/10.3390/photochem4010001