Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives†

doi:10.7503/cjcu20150034

Abstract

Abstract:

Four novel symmetrical 4,4'-difluoro-4-bora-3a,4a-diaza-sindacene(BODIPY) derivatives were synthesized. These BODIPY derivatives bear different donor or acceptor units as conjugate bridge, and the BODIPYs meso-position substituted by thiophene or benzene as the termini groups. The structures of all the compounds were identified by ¹H NMR, ¹³C NMR and MS techniques. The photophysical properties of these compounds were measured by the UV-Vis absorption and the fluorescence emission spectrophotometer. And the electrochemical properties were investigated by the cyclic voltammetry. The results of absorption spectra confirmed that these BODIPYs had a characteristic absorption peak, and the conjugate bridges had little influence on the intramolecular charge-transfer(ICT) interaction neither used as donor nor acceptor. On the other hand, meso-position substituentes have a weak influence on the ICT interaction in the BODIPYs, and meso-position thiophene substituted ones have raised more intensive ICT than the meso-position benzene substituted ones. Both the absorption spectra and cyclic voltammetry data indicate that BODIPYs with meso-thiophene substitutuents possess a lower oxidation potential and a narrower band gap than those meso-position benzene ones.

Key words: 4, 4'-Difluoro-4-bora-3a, 4a-diaza-sindacene(BODIPY) derivative, Conjugate bridge, Donor or acceptor unit, Photophysical property

CLC Number:

O621

TrendMD:

PENG Zaixi, LIAO Junxu, XU Yongjun, ZHAO Hongbin, PENG Min, CUI Yunzeng, NING Jingheng. Synthesis and Properties of Symmetrical Donor or Acceptor Unit Conjugate Linked BODIPY Derivatives^†[J]. Chem. J. Chinese Universities, 2015, 36(6): 1094.

Figures/Tables 6

Scheme 1 Synthetic routes of compounds BDP1—BDP4

Table 1 Appearance, yields and melting points and MALDI-TOF-MS data for compounds BDP1—BDP4

Compd.	Appearance	Yield^*(%)	m. p./℃	MALDI-TOF-MS(calcd.), m/z
BDP1	Purple red solid	51.0	247—249	978.359(978.400)
BDP2	Blue solid	56.0	183—185	990.294(990.310)
BDP3	Orange red crystal	61.0	159—162	649.203(668.170)
BDP4	Blue purple solid	57.0	188—190	661.084(680.090)

Table 2 1H NMR and 13C NMR data for compounds BDP1—BDP4

Compd.	¹H NMR(600 MHz, CDCl₃), δ	¹³C NMR(151 MHz, CDCl₃), δ
BDP1	8.00(s, 4H), 7.94(d,J=8.2 Hz, 4H), 7.86(s, 2H), 7.71(d, J=8.2 Hz, 4H), 7.05(d, J=4.0 Hz, 4H), 6.61(d, J=4.0 Hz, 4H), 4.31(d, J= 5.5 Hz, 4H), 1.70(m, 2H), 1.27—1.22(m, 16H), 1.05—0.97(m, 12H)	146.48, 144.85, 144.27, 142.33, 136.87, 134.83, 133.74, 132.98, 131.32, 129.74, 126.36, 126.08, 118.63, 117.31, 40.73, 30.63, 29.68, 29.23, 24.03, 23.23, 14.07, 11.44
BDP2	7.98(s, 4H), 7.70(s, 2H), 7.60(d, J=3.9 Hz, 2H), 7.51(d, J=3.8 Hz, 2H), 7.40(d, J=4.1 Hz, 4H), 6.64(d, 4H), 4.27(d, J=5.4 Hz, 4H), 1.90(m, 2H), 1.41—1.20(m, 12H), 1.10—0.98(m, 12H)	144.67, 143.93 143.66 138.68, 125.50, 134.52, 134.24, 134.10, 132.76, 131.07, 129.61, 126.36, 118.58, 118.13, 40.74, 30.60, 29.66, 29.26, 23.83, 23.18, 14.28, 11.43
BDP3	8.24(d,J=8.1 Hz, 4H), 8.01(s, 4H), 8.00(s, 2H), 7.82(d, J=8.1 Hz, 4H), 7.11(d, J=4.0 Hz, 4H), 6.62(d, J=2.8 Hz, 4H)	153.93, 146.74, 144.32, 139.76, 134.95, 134.01, 132.76, 131.59, 130.92, 129.34, 128.56, 118.68
BDP4	8.28(d,J=4.0 Hz, 2H), 8.08(s, 2H), 7.97(s, 4H), 7.71(d, J=3.8 Hz, 2H), 7.42(d, J=3.5 Hz, 4H), 6.63(d, 4H)	151.42, 146.93, 143.35, 135.19, 132.27, 131.21, 130.53, 127.46, 125.35, 123.94, 122.10, 119.07

Table 3 Optical data of BDPs in dichloromethane solution and thin film on quartz surface

Compd.	$λ max a$ /nm	lgε_max	λ_max ^b/nm	λ_em/nm	Stokes-shift/cm^-1
BDP1	503	4.84	520	522	723.6
BDP2	516	4.33	536	556	1394.2
BDP3	503	4.98	530	533	1119.0
BDP4	517	5.91	571	614	3055.7

Table 3 Optical data of BDPs in dichloromethane solution and thin film on quartz surface

Compd.	$λ max a$ /nm	lgε_max	λ_max ^b/nm	λ_em/nm	Stokes-shift/cm^-1
BDP1	503	4.84	520	522	723.6
BDP2	516	4.33	536	556	1394.2
BDP3	503	4.98	530	533	1119.0
BDP4	517	5.91	571	614	3055.7

Fig.1 Optimized structures of compounds BDP1—BDP4

Table 4 Electrochemistry data of compounds BDPs*

Compd.	E_g/eV	$E onset red$ /V	$E p red$ /V	E_ox/V	E_HOMO/eV	E_LUMO/eV
BDP1	2.13	-0.78	-1.04	1.35	-5.62	-3.49
BDP2	1.85	-0.74	-1.01	1.11	-5.38	-3.53
BDP3	2.29	-0.66	-1.03	1.63	-5.95	-3.66
BDP4	1.97	-0.70	-1.04	1.27	-5.54	-3.57

Table 4 Electrochemistry data of compounds BDPs*

Compd.	E_g/eV	$E onset red$ /V	$E p red$ /V	E_ox/V	E_HOMO/eV	E_LUMO/eV
BDP1	2.13	-0.78	-1.04	1.35	-5.62	-3.49
BDP2	1.85	-0.74	-1.01	1.11	-5.38	-3.53
BDP3	2.29	-0.66	-1.03	1.63	-5.95	-3.66
BDP4	1.97	-0.70	-1.04	1.27	-5.54	-3.57

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