Читать книгу Handbook of Aggregation-Induced Emission, Volume 1 - Группа авторов - Страница 41

Resonance Raman spectroscopy (RRS) is a spectroscopic technique in which the incident laser frequency is close to the electronic transition of chromophore. RRS is able to provide the information of excited‐state properties. Under the Franck−Condon approximation and resonance condition, the RRS intensity σ(ω_j) from the jth normal mode is proportional to reorganization energy λ_j times frequency ω_j: σ ∝ ω_jλ_j → σ/ω_j ∝ λ_j [58, 59]. As discussed above, the reorganization energy is one key factor to determine k_ic, which plays an important role in the AIE mechanism. In this part, we use RRS to detect the aggregation effect on the reorganization energy during the nonradiative process and validates the above‐proposed AIE mechanism.

The AIEgen HPDMCb [60] and AIE‐inactive DCPP [55] (see Figure 2.3) were chosen as models to show the connection between RRS intensity and the reorganization energy [61]. By combining PCM and QM/MM models, the photophysical properties of these two compounds were studied in both solution and solid phases. It is found that the k_r of HPDMCb is similar in both phases; while k_ic decreases by 4 orders of magnitude from 1.31 × 10¹¹ to 2.29 × 10⁷ s⁻¹ upon aggregation, the corresponding Φ_F increases to 78.0% from 0.07%, well consistent with the experimental results (see Table 2.5) [60]. For AIE‐inactive DCPP, the radiative and nonradiative decay rates and Φ_F are insensitive to the aggregation (see Table 2.5). Analyzing the three factors for the nonradiative decay rate, it is found that both the nonadiabatic coupling and adiabatic energy gap are almost unchanged for HPDMCb and DCPP. Moreover, the reorganization energy of DCPP has a little change from solution to solid phase. Thus, the excited‐state decay process of DCPP is independent on the surrounding environment. Much differently, the reorganization energy of HPDMCb is significantly reduced from solution to solid phase, as shown in Figure 2.6a, which leads to the large decrease of k_ic and the obvious increase of Φ_F in the solid phase. From Figure 2.6a, it is also seen that the frequencies of the low‐frequency modes (<100 cm⁻¹) become ca. two to threefold larger upon aggregation; however, the reorganization energy of each mode reduces a lot. These suggest that the coupling between low‐frequency modes and the transition electrons is strongly decoupled upon aggregation, leading to the decrease of nonradiative decay rate. With the incident wavelength equal to the adiabatic excitation energy, the RRS plot of HPDMCb in both solution and solid phases is shown in Figure 2.6b, and the blue shift of the low‐frequency peaks with the relatively decreased RRS intensity fully reflects the change character of the reorganization energies. In addition, the high‐frequency normal modes are almost unresponsive to the environment, as shown in both reorganization energies and RRS signals for AIE‐active HPDMCb. Therefore, the above‐proposed AIE mechanism is successfully confirmed by RRS signals and the RRS can act as a good detection means of AIE property.

Table 2.4 The calculated spectral properties and reorganization energies corrected by zero‐point energy for DSA, DCDPP, and TPBD in solution and aggregate phase, respectively.

Source: © 2014 Royal Society of Chemistry.

Unit: eV	Absorption	Emission	Stokes shift	Reorganization energy
						κ sol	κ agg
DSA [57]	2.82	2.75	0.07	2.18	2.01	0.17	0.74	0.64	0.74	0.64
DCDPP [57]	3.36	3.24	0.12	2.53	2.19	0.34	1.05	0.83	1.05	0.83
TPBD [57]	3.72	3.55	0.17	2.98	2.51	0.47	1.04	0.74	1.03	0.73

Table 2.5 Calculated k_r, k_ic, and Φ_F in both solution and aggregate phases at room temperature for HPDMCb and DCPP, respectively.

	k r (s−1)	k ic (s−1)	Φ F (%)	k r (s−1)	k ic (s−1)	Φ F (%)
	In isolated state	In solid phase
HPDMCb [61]	8.64 × 107	1.31 × 1011	0.07	7.95 × 107	2.29 × 107	78.0
DCPP [61]	7.98 × 106	1.01 × 106	88.8	3.30 × 106	0.61 × 106	84.4