Mechanofluorochromic materials, which are dependent on changes in physical molecular packing modes, have attracted considerable interest over the past ten years. In this review, recent progress in the area of pure organic mechanofluorochromism is summarized, and majority of the reported organic mechanofluorochromic systems are discussed, along with their derived structure–property relationships. The existence of a structural relationship between aggregation-induced emission compounds and mechanofluorochromism is recognized based on our recent results, which considered aggregation-induced emission compounds as a well of mechanofluorochromic materials. The established structure–property relationship will guide researchers in identifying and synthesizing more mechanofluorochromic materials.

Recent advances in organic mechanofluorochromic materials

Functional π-Gelators and Their Applications

The possibility to change the molecular assembled structures of organic and organometallic materials through mechanical stimulation is emerging as a general and powerful concept for the design of functional materials. In particular, the photophysical properties such as photoluminescence color, quantum yield, and emission lifetime of organic and organometallic fluorophores can significantly depend on the molecular packing, enabling the development of molecular materials with mechanoresponsive luminescence characteristics. Indeed, an increasing number of studies have shown in recent years that mechanical force can be utilized to change the molecular arrangement, and thereby the optical response, of luminescent molecular assemblies of π-conjugated organic or organometallic molecules. Here, the development of such mechanoresponsive luminescent (MRL) molecular assemblies consisting of organic or organometallic molecules is reviewed and emerging trends in this research field are summarized. After a brief introduction of mechanoresponsive luminescence observed in molecular assemblies, the concept of "luminescent molecular domino" is introduced, before molecular materials that show turn-on/off of photoluminescence in response to mechanical stimulation are reviewed. Mechanically stimulated multicolor changes and water-soluble MRL materials are also highlighted and approaches that combine the concept of MRL molecular assemblies with other materials types are presented in the last part of this progress report.

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Mechanoresponsive Luminescent Molecular Assemblies: An Emerging Class of Materials

It has been difficult to decipher the mechanistic issue whether E/Z isomerization is involved in the aggregation-induced emission (AIE) process of a tetraphenylethene (TPE) derivative, due to the difficulty in the synthesis of its pure E and Z conformers. In this work, pure stereoisomers of a TPE derivative named 1,2-bis{4-[1-(6-phenoxyhexyl)-4-(1,2,3-triazol)yl]phenyl}-1,2-diphenylethene (BPHTATPE) are successfully synthesized. Both isomers show remarkable AIE effect (αAIE ≥ 322) and high fluorescence quantum yield in the solid state (ΦF 100%). The conformers readily undergo E/Z isomerization upon exposure to a powerful UV light and treatment at a high temperature (>200 °C). Such conformational change, however, is not observed under normal fluorescence spectrum measurement conditions, excluding the involvement of the E/Z isomerization in the AIE process of the TPE-based luminogen. The molecules of (E)-BPHTATPE self-organize into ordered one-dimensional nanostructures such as microfibers and nanorods that...

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Click Synthesis, Aggregation-Induced Emission, E/Z Isomerization, Self-Organization, and Multiple Chromisms of Pure Stereoisomers of a Tetraphenylethene-Cored Luminogen

Mechanochromic fluorescence (MCF) materials are a sort of smart material whose photophysical properties are sensitive to mechanical stimulation, such as photoluminescence color, fluorescence quantum yield and emission lifetime. Recently, an increasing number of studies have shown that these photophysical properties can be affected greatly by the molecular packing and conformation, enabling the rapid development of functional materials with mechanochromic fluorescence properties. In this review, we focus on MCF materials with distinct emission properties and various molecular arrangements, especially the inherent correlation between molecular packing modes and emissive behaviors. Many of the selected representative examples possess polymorphism, offering the possibility of exploring different emissions from the exact molecular packing in single crystals. Correspondingly, some remarks are made on the outlook for the next developments in MCF materials and the required thinking about the structure–packing–performance relationship.

Molecular conformation and packing: their critical roles in the emission performance of mechanochromic fluorescence materials

Mechanofluorochromic or piezochromic fluorescence chemistry involves the switching and tuning of the luminescent properties of solid-state materials induced by exogenous forces, such as grinding, shearing, compression, tension, and so forth. Up until now, most reported mechanochromic systems, including liquid crystals, organic molecules, organometallic compounds, polymers, and dye-doped polymers, have displayed reversible two-color changes, which arise from either supramolecular or chemical structure transformations. However, fluorescent materials that undergo mechanically induced multicolor changes remain rare; this Minireview is focused on such materials. Topics are categorized according to the different applied forces that are required to induce the multicolor change, including mechanical control of either the supramolecular structures or the chemical structures, and mechanical control of both the supramolecular structures and chemical structures.

Mechanically Induced Multicolor Change of Luminescent Materials.

Asserting its independence: A single organic molecule containing pyrene and rhodamine B chromophores separated by a peptide spacer formed a mechanochromic material whose fluorescence could be switched from blue to bluish-green and reddish by grinding. Modulation of the overlapped packing pattern of the pyrene excimer for blue emission was crucial for the reversible tricolored switching observed.

Mechanically Induced Multicolor Switching Based on a Single Organic Molecule

A smart luminescent material whose emission color and emission intensity can be separately modulated by external force is demonstrated. The rational manipulation of rich noncovalent interactions and fluorophore packing style promotes an in-depth understanding between supramolecular structure and photophysical property and offers an effective strategy to modulate the light-emitting property in a predicative way.

Reversible tuning luminescent color and emission intensity: a dipeptide-based light-emitting material.

Color schemes: A mechanochromic material composed of two types of peptides bearing a pyrene group and rhodamine B moieties, respectively, displays multiluminescent colors, such as blue, green, and reddish in one sample (see picture). The mechanochromic behavior is based on a combined switching of molecular assemblies and chemical structure.

Mingjun Teng

Papers

Mechanically Induced Multicolor Change of Luminescent Materials.

Mechanically Induced Multicolor Switching Based on a Single Organic Molecule

Reversible tuning luminescent color and emission intensity: a dipeptide-based light-emitting material.

A Dipeptide‐Based Multicolored‐Switching Luminescent Solid Material: When Molecular Assemblies Meet Mechanochemical Reaction

Mechanochromic luminescent property of a polypeptide-based dendron.