Handbook of Aggregation-Induced Emission, Volume 1. Группа авторов

k_r, k_ic, and IE of five AIEgens (HPS [37], BtTPS [65], HPDMCb [60], TPBD [56], and DPTDTP [66]) and four non‐AIEgens (BPS [67], perylene [68], DSB [69], and anthracene [68]) in both solution and solid states were calculated by combining the PCM and hybrid QM/MM models, respectively [64]. As shown in Table 2.6, it is found that the k_ic decreases sharply by several orders of magnitude from the solution to solid phase for AIEgens but suffers a tiny change for non‐AIEgens. As shown in Figure 2.7b, it is found that (i) the IE for all cases is negative; (ii) for AIEgens, the IE is minor in solution (~10%) but becomes remarkable in solid phases (~65–95%); (iii) for non‐AIEgens, the IE results in both solution and solid phases are close to each other and fall in the range of −40 to −90%. The calculated isotopic characteristic of AIEgens is further verify by experiments for HPS before and after deuteration; the experimental IEs well reproduce the calculated results with very little IE in solution but remarkably in solid phase. Thus, the proposed IE scheme further verifies the AIE mechanism theoretically and experimentally in which the nonradiative decay channels are blocked greatly owing to the decoupling of vibration–vibration and electron–vibration and then turning the fluorescence on.

Figure 2.7 (a) Representation of the isotope effect on k_ic. (b) IE results for AIEgens and non‐AIEgens.

      Source: Reproduced from Ref. [64]. Copyright 2016 The Royal Society of Chemistry.

      2.4.4 Linear Relationship between Fluorescence Intensity and Amorphous Aggregate Size

As the major existing form of AIEgens in experiments, the AIE mechanism of amorphous aggregate is rarely studied theoretically and is a great challenge because of their structural heterogeneity. Here, we proposed a theoretical protocol combining MD simulations and quantum mechanics/molecular mechanics calculations, and the TVCF spectrum and rate theory, to quantitatively investigate the AIE property in amorphous state and explore the relationship between molecular packing, optical spectra, and fluorescence quantum efficiency [70]. Take HPS [37] as an example; amorphous aggregates with five different sizes were set up in aqueous solution to demonstrate clearly the relationship between molecular packing, optical spectra, and Φ_F, as well as their size effect. MD simulations indicate that HPS aggregates are generally near‐spherical and the packing density of aggregates is size‐independent and smaller than that of crystals (Figure 2.8a, b). Due to the structural heterogeneity of the aggregates, AIEgen in amorphous aggregate could not be represented by an aggregate of the solely fixed conformation. Thus, at each size, five embedded and one exposed QM/MM models were set up for all sizes of aggregates. As shown in Figure 2.8c, the absorption of amorphous aggregates is similar to that of crystals, while the emission is clearly red‐shifted from the crystalline one. This can be explained by the lower‐packing‐density‐induced larger reorganization energies in amorphous HPS aggregates than that in crystal. Strikingly, Φ_F of the embedded HPS is size‐independent and about 1 or 2 orders of magnitude larger than those of the exposed ones (<7%), see Figure 2.8d. In addition, k_r is insensitive to environments, k_ic is very sensitive to the environment, and k_ic of embedded HPS molecules are 2–4 orders of magnitude smaller than those of the exposed ones because of the restriction of the intramolecular low‐frequency rotational motions of embedded HPS molecules. More excitingly, the size‐independent Φ_F predicts a linear relationship between the fluorescence intensity and aggregate size of the nanosized HPS aggregates. This indicates that the electron–vibration and vibration–vibration coupling are dependent on the compactness of molecular packing other than the size of the aggregate. In addition, the crystallization‐enhanced emission phenomenon in the experiment can be explained by the calculated blue‐shifted emission and enhanced fluorescence intensity of HPS from amorphous aggregate to the crystalline phase.

Table 2.6 Calculated room‐temperature k_ic (s⁻¹) for nondeuterated (H‐all) and fully deuterated (D‐all) isotopomers of the AIEgens and nonAIEgens in both solution and solid phases.

      Source: © 2016 Royal Society of Chemistry [64].

	Solution	Solid	Solution	Solid	Solution	Solid
	HPS		BtTPS		HPDMCb
H‐all	2.44 × 10^11	8.58 × 10^6	2.20 × 10^11	2.73 × 10^7	1.31 × 10^11	2.26 × 10^7
D‐all	2.22 × 10^11	2.61 × 10^6	1.97 × 10^11	6.89 × 10^6	1.27 × 10^11	7.11 × 10^6
IE	–9.0%	–69.6%	–10.5%	–74.8%	–3.1%	–68.5%
	TPBD		DPTDTP		BPS
H‐all	2.16 × 10^10	4.21 × 10^6	1.79 × 10^9	6.76 × 10^5	1.13 × 10^10	2.19 × 10^9
D‐all	1.96 × 10^10	2.77 × 10^5	1.61 × 10^9	2.23 × 10^5	7.05 × 10^9	1.44 × 10^9
IE	–9.3%	–93.4%	–10.1%	–67.0%	–37.6%	–34.2%
	Perylene		DSB