Stability of Rhodamine Lactone Cycle in Solutions: Chain–Ring Tautomerism, Acid–Base Equilibria, Interaction with Lewis Acids, and Fluorescence
Abstract
:1. Introduction
2. Results and Discussion
2.1. Identification of the Equilibrium Structures in Solution
2.2. The Influence of Molecular Structure of Rhodamine Dyes on the Chain–Ring Tautomerism
2.3. The Acidic Dissociation of the HR+ Acid and the Charge Type of the Acid/Base Couple
Solvent | Rhodamine B (1) | Rhodamine 19 (N,N′-Diethyl-2,7-Dimethylrhodamine) | Rhodamine 5 |
---|---|---|---|
Water | 3.2 b; 3.22 c; 3.22 d; 3.41 e; 3.46 f; 3.36 g | 3.15 h; 3.26 i | 3.10 |
Methanol | 7.6 j; 7.4 k | — | — |
Ethanol | 8.7 j; 8.7 k | 9.4 h | — |
N,N-Dimethylformamide | 6.5 k | — | — |
N-Methyl pyrrolidine-2-one | 5.55 l | — | — |
91.3 mass% DMSO | 5.60 k | — | — |
Acetone + 5 mol% DMSO | 7.50 m | 7.90 m | — |
90 mass% Acetone | 6.47 k | — | 7.31 |
2.4. Tautomerism: Influence of the Solvent Nature
2.5. Interactions with Electrolytes
2.6. Fluorescence and Photocleavage of the Lactone Cycle
3. Experimental
3.1. Materials
3.2. Synthesis of Dyes 13–15
3.3. Apparatus
3.4. Procedure
3.5. Quantum-Chemical Calculations
4. Conclusions
Author Contributions
Funding
Informed Consent Statement
Conflicts of Interest
References
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Atom | Lactone R0 | Zwitterion R± |
---|---|---|
1 | 128.41 | 132.62 |
2 | 105.50 | 114.16 |
3 | 144.43 | 155.95 |
4 | 96.95 | 96.58 |
5 | 105.59 | 106.23 |
6 | 134.97 | 153.19 |
7 | 117.41 | 125.35 |
8 | 124.63 | 128.46 |
9 | 79.16 | 173.33 |
10 | 106.32 | 114.36 |
11 | 147.75 | 154.17 |
12 | 149.23 | 158.74 |
13 | 108.37 | 115.17 |
14 | 168.78 | 161.69 |
1′ | 152.76 | 133.82 |
2′ | 127.25 | 141.42 |
3′ | 124.26 | 130.93 |
4′ | 129.70 | 130.63 |
5′ | 124.63 | 130.43 |
6′ | 124.26 | 130.54 |
Atoms | Cation HR+ of 1 | Esters of 1 | R± of 1 | R0 of 1 | |
---|---|---|---|---|---|
From Ref. [60] | From Ref. [64] | From Ref. [60] | From Ref. [60] | ||
CD3OD | DMSO(d6) | CDCl3 | CD3OD + NaOH | DMSO(d6) + NaOH | |
1, 8 | 131.7 | 131.9 | 131.1–131.3 | 132.4 | — |
2, 7 | 114.7 | 115.2 | 114.2–114.9 | 114.1 | 109.2 |
3, 6 | 158.6 | 157.4 | 154.9–155.8 | 158.6 | 150.2 |
4, 5 | 97.0 | 97.0 | 96.3–95.4 | 96.3 | 97.9 |
11, 12 | 156.4 | 155.8 | — | 156.1 | 153.7 |
10, 13 | 114.2 | 113.5 | — | 114.2 | 106.1 |
9 | 160.3 | – | 158.7–158.9 | 162.5 | — |
14 | 167.2 | 167.4 | 164.9–165.5 | 172.8 | 169.9 |
1′ | – | 134.2 | 133.2–133.5 | 133.1 | — |
2′ | 133.2 | 135.4 | 129.7–130.3 | 141.0 | — |
No. | Compound | /nm | KT = [R0]/[R±] | ||
---|---|---|---|---|---|
HR+ | R± | ||||
1 | 550 | 540 | 10 (337) | 16.6 [58] | |
2 | 552 | 540 | 12 (402) | 16.9 | |
3 | 551 | 538 | 13 (438) | 29.8 | |
4 | 531 | 515 | 16 (585) | 2.19 | |
5 | 565 | 555 | 10 (319) | 1.05 | |
6 | 577 | 566 | 11 (337) | 0.32 | |
7 | 578 | 566 | 12 (367) | 0.38 | |
8 | 575 | – a | – | – | |
9 | 522 | – a | – | – | |
10 | 576 | – a | – | – | |
11 | 494, 525 | – a | – | – | |
12 | 542 | 470 | 72 (2826) | 4.04 | |
13 | 558 | 546 | 12 (394) | 4.10 | |
14 | 562 | 550 | 12 (483) | 1.65 | |
15 | 583 | 573 | 10 (299) | 0.12 |
Solvent | KT = [R0]/[R±] |
---|---|
Water | 0.005–0.01 a,b |
Methanol | 0.1 c |
Ethanol | 0.28 d |
90 mass% aqueous acetone | 16.6 |
91.3 mass% aqueous DMSO | 59 e |
CHCl3 saturated with water | 90 f |
N,N-Dimethylformamide | 100 g |
98.3 mass% aqueous acetone | 234 h |
Acetone | 250 a |
Solvent a | /nm | KT | |||
---|---|---|---|---|---|
HR+ | R b | ||||
Methanol (32) | 564 | 556 | 8 | 0.028 | 0.762 |
Benzene—ethanol—water c (12.8) | 567 | 556 | 11 | 0.155 | 0.587 |
1-Propanol (20.4) | 566 | 556 | 10 | 0.16 | 0.617 |
1-Butanol (17.4) | 564 | 553 | 11 | 0.19 | 0.586 |
2-Methyl-propane-1-ol (17.9) | 566 | 554 | 12 | 0.23 | 0.552 |
2-Propanol (19.9) | 564 | 550 | 14 | 0.32 | 0.546 |
2-Methyl-propane-2-ol (12.5) d | 563 | 546 | 17 | 2.94 | 0.389 |
90% Acetone—10% water e (24) | 565 | 555 | 10 | 1.06 | 0.57 |
95% Acetone—5% water e (22) | 568 | 560 | 8 | 5.76 | 0.49 |
90% CH3CN—10% water e (39.4) | 567 | 558 | 9 | 0.17 | 0.692 |
CH3CN (35.9) | 566 | 550 | 9 | 48.3 | 0.460 |
91.3% DMSO e (56) | 574 | 560 | 14 | 2.89 | 0.50 |
DMSO (46.4) | 577 | 566 | 11 | 70.7 | 0.444 |
N,N-Dimethylformamide (36.7) | 570 | 555 | 5 | 89.9 | 0.404 |
Solvent | Cation HR+ (0.01 M H2SO4) | Neutral Form (R± ⇄ R0) (0.02 M DBU) | ||
---|---|---|---|---|
λmax, nm | Emax × 10−3, M−1 cm−1 | λmax, nm | Emax × 10−3, M−1 cm−1 | |
Methanol | 564 | 98.0 | 556 | 95.3 |
Acetonitrile | 566 | 98.6 | 550 | 2.00 |
DMF | 570 | 110.0 | 555 | 1.21 |
DMSO | 575 | 93.2 | 556 | 1.30 |
Solvent | ||||
---|---|---|---|---|
Methanol | 9.40 | +1.52 | 3.68 | −1.55 |
90% acetonitrile (x2 = 0.798) | 9.1 | +1.21 | 3.70 | −0.77 |
2-Propanol | 11.75 | +1.42 | 6.13 | −0.49 |
91% DMSO (x2 = 0.708) | 8.05 | −3.61 | 7.46 | +0.48 |
Acetonitrile | 20.7 | +7.85 | 8.65 | +1.68 |
DMF | 12.3 | –2.52 | 9.78 | +1.95 |
DMSO | 11.1 | –3.40 | 10.3 | +1.85 |
Transition | Wavelength, Wavenumber, Oscillator Strength | Electronic Localization Indices | Charge Transfer Indices | ||
---|---|---|---|---|---|
Absorption (S0-state optimized geometry, DFT) | |||||
S0-S1 | 352 nm 28,400 cm−1 0.005 | 24.7 | 24.7 | 50.6 | |
S0-S2 | 342 nm 29,200 cm−1 0.0004 | 22.2 | 22.2 | 54.1 | |
Fluorescence (S1-state optimized geometry, TDDFT) | |||||
S0-S1 | 496 nm 20,150 cm−1 0.005 | 4.2 | 44.1 | 51.2 |
Compound | , nm (from Absorption Spectrum) | , nm | Stokes Shift, cm−1 |
---|---|---|---|
2 | 313 | 450 | 9700 |
3 | 310 | 454 | 10,300 |
4 | 301 | 389 | 7500 |
5 | 312 | 478 | 11,150 |
6 | 318 | 486 | 10,900 |
7 | 319 | 491 | 11,050 |
9 | 325 | 456 | 8850 |
10 | 315 | 462 | 10,100 |
12 | 351 | 485 | 7900 |
14 | 341 | 511 | 9750 |
15 | 310 | 435 a | 9300 |
585 b | 15,200 |
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Obukhova, O.M.; Mchedlov-Petrossyan, N.O.; Vodolazkaya, N.A.; Patsenker, L.D.; Doroshenko, A.O. Stability of Rhodamine Lactone Cycle in Solutions: Chain–Ring Tautomerism, Acid–Base Equilibria, Interaction with Lewis Acids, and Fluorescence. Colorants 2022, 1, 58-90. https://0-doi-org.brum.beds.ac.uk/10.3390/colorants1010006
Obukhova OM, Mchedlov-Petrossyan NO, Vodolazkaya NA, Patsenker LD, Doroshenko AO. Stability of Rhodamine Lactone Cycle in Solutions: Chain–Ring Tautomerism, Acid–Base Equilibria, Interaction with Lewis Acids, and Fluorescence. Colorants. 2022; 1(1):58-90. https://0-doi-org.brum.beds.ac.uk/10.3390/colorants1010006
Chicago/Turabian StyleObukhova, Olena M., Nikolay O. Mchedlov-Petrossyan, Natalya A. Vodolazkaya, Leonid D. Patsenker, and Andrey O. Doroshenko. 2022. "Stability of Rhodamine Lactone Cycle in Solutions: Chain–Ring Tautomerism, Acid–Base Equilibria, Interaction with Lewis Acids, and Fluorescence" Colorants 1, no. 1: 58-90. https://0-doi-org.brum.beds.ac.uk/10.3390/colorants1010006