High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent

Monika Gupta; Priyadarshini Kamble; M. C. Rath; D. B. Naik; Alok K. Ray

doi:10.1364/AO.54.007013

Applied Optics
Vol. 54,
Issue 23,
pp. 7013-7019
(2015)
•https://doi.org/10.1364/AO.54.007013

High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent

Monika Gupta, Priyadarshini Kamble, M. C. Rath, D. B. Naik, and Alok K. Ray

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Monika Gupta, Priyadarshini Kamble, M. C. Rath, D. B. Naik, and Alok K. Ray, "High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent," Appl. Opt. 54, 7013-7019 (2015)

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Abstract

Many pyrromethene (PM) dyes have been shown to outperform established rhodamine dyes in terms of laser efficiency in the green-yellow spectral region, but their rapid photochemical degradation in commonly used ethanol or methanol solvents continues to limit its use in high average power liquid dye lasers. A comparative study on narrowband laser efficiency and photostability of commercially available PM567 and PM597 dyes, using nonpolar n-heptane and 1,4-dioxane and polar ethanol solvents, was carried out by a constructed pulsed dye laser, pumped by the second harmonic (532 nm) radiation of a $Q$ -switched Nd:YAG laser. Interestingly, both nonpolar solvents showed a significantly higher laser photostability ( $\sim 100$ times) as well as peak efficiency ( $\sim 5 %$ ) of these PM dyes in comparison to ethanol. The different photostability of the PM dyes was rationalized by determining their triplet-state spectra and capability to generate reactive singlet oxygen ( ${}^{1}{O_{2}}$ ) by energy transfer to dissolved oxygen in these solvents using pulse radiolysis. Heptane is identified as a promising solvent for these PM dyes for use in high average power dye lasers, pumped by copper vapor lasers or diode-pumped solid-state green lasers.

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Dye	Solvent	$λ_{abs}$ ^a (nm)	$E_{\max}$ ^b ( $10^{4} M^{- 1} {cm}^{- 1}$ )	$λ_{em}$ ^c (nm)	$Φ_{fl}$ ^d	$ν ({cm}^{- 1})$	$τ_{fl}$ ^e (ns)	$k_{r}$ ^f ( $s^{- 1}$ ) ( $10^{8}$ )	$k_{nr}$ ^g ( $s^{- 1}$ ) ( $10^{8}$ )
PM567	ethanol	518.0	7.1	533.0	0.84^f	543	6.48	1.3	0.25
	1,4-dioxane	518.0	6.2	535.0	0.89	613	6.52	1.4	0.17
	n-heptane	521.0	9.1	535.0	0.97	502	6.12	1.6	0.05
PM597	ethanol	524.0	6.8	556.0	0.42^f	1098	4.04	1.0	1.4
	1,4-dioxane	525.0	6.6	558.0	0.55	1126	4.37	1.3	1.03
	n-heptane	526.0	8.3	557.0	0.48	1058	4.83	0.99	1.1

Dye	Solvent	[Dye] (mM)	$λ_{L}$ ^a [nm]	Tuning Range [nm]	$η$ ^b [%]
PM567	ethanol	1.0	553.8	541–583	15.3
	1,4-dioxane	1.2	555.8	540–584	17.1
	n-heptane	1.3	556	540–586	18.8
PM597	ethanol	0.5	579	560–625	13.4
	1,4-dioxane	0.6	578	560–625	17.0
	n-heptane	0.7	578	560–625	18.6

Dye	Solvent	$Φ_{pd}$ ^a	$Φ_{pd heptane}^{- 1} / Φ_{pd ethanol}^{- 1}$	$Φ_{pd dioxane}^{- 1} / Φ_{pd ethanol}^{- 1}$	$Φ_{pd PM 597}^{- 1} / Φ_{pd PM 567}^{- 1}$	$Φ_{pd DABCO}$	$Φ_{pd DABCO}^{- 1} / Φ_{pd}^{- 1}$
PM567	ethanol	$6.7 \times 10^{- 4}$	–	–	–	$1.5 \times 10^{- 4}$	4.5
	1,4-dioxane	$3.1 \times 10^{- 5}$	–	21.3	–	$1.5 \times 10^{- 5}$	2.1
	n-heptane	$7.3 \times 10^{- 6}$	90.7	–	–	$5.0 \times 10^{- 6}$	1.5
PM597	ethanol	$2.8 \times 10^{- 4}$	–	–	2.4	$6.9 \times 10^{- 5}$	4.1
	1,4-dioxane	$2.7 \times 10^{- 6}$	–	103.7	11.5	$2.4 \times 10^{- 6}$	1.1
	n-heptane	$2.8 \times 10^{- 6}$	100	–	2.6	$1.2 \times 10^{- 6}$	2.3

Dye	Solvent	$λ_{\max T}$ [nm]	$ε_{\max T}$ ^a $[M^{- 1} {cm}^{- 1}]$	$k [^{3} Dye \to O_{2}]$ $[10^{8} M^{- 1} S^{- 1}]$
PM567	1,4-dioxane	710	2440	8.7
PM567	n-heptane	710	2280	8.5
PM597	1,4-dioxane	700	2630	5.2
PM597	n-heptane	700	2340	4.8

Dye	Solvent	$λ_{abs}$ ^a (nm)	$E_{\max}$ ^b ( $10^{4} M^{- 1} {cm}^{- 1}$ )	$λ_{em}$ ^c (nm)	$Φ_{fl}$ ^d	$ν ({cm}^{- 1})$	$τ_{fl}$ ^e (ns)	$k_{r}$ ^f ( $s^{- 1}$ ) ( $10^{8}$ )	$k_{nr}$ ^g ( $s^{- 1}$ ) ( $10^{8}$ )
PM567	ethanol	518.0	7.1	533.0	0.84^f	543	6.48	1.3	0.25
	1,4-dioxane	518.0	6.2	535.0	0.89	613	6.52	1.4	0.17
	n-heptane	521.0	9.1	535.0	0.97	502	6.12	1.6	0.05
PM597	ethanol	524.0	6.8	556.0	0.42^f	1098	4.04	1.0	1.4
	1,4-dioxane	525.0	6.6	558.0	0.55	1126	4.37	1.3	1.03
	n-heptane	526.0	8.3	557.0	0.48	1058	4.83	0.99	1.1

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Applied Optics