An organic molecular glass having room temperature phosphorescence and photochromism and a preparation method thereof

Abstract

The application discloses an organic molecular glass with room-temperature phosphorescence and photochromism, which comprises the following components by weight: 1-7 parts of a phosphorescent guest compound, 1-7 parts of a photochromic guest compound and 200-4000 parts of a molecular glass host compound. The molecular glass prepared by the application realizes photochromism and phosphorescence, and the molecular glass has the dual optical properties of photochromism and room-temperature phosphorescence, can integrate the application advantages of the two, improves the material technical content and added value, and expands high-end application scenarios. Meanwhile, the multiple recognition mechanisms are constructed by means of multi-signal synergistic response, so that the value of practical application is ensured. Finally, large-scale industrial preparation of 30 cm*30 cm doped glass is realized, and the prepared doped glass still has excellent optical properties.

Description

Technical Field

[0001] This invention relates to the field of molecular glasses, and more specifically to an organic molecular glass exhibiting room temperature phosphorescence and photochromism. Background Technology

[0002] Room temperature phosphorescence (RTP) and photochromism are optical properties with very different characteristics but wide applications: room temperature phosphorescence produces a lasting afterglow by intersystem crossing of excited states and is used in anti-counterfeiting, biomedical diagnosis and treatment, optoelectronic devices and other fields; while photochromism undergoes a sensitive and significant color change under light stimulation and is suitable for optical switches, advanced anti-counterfeiting, optical data storage and other scenarios.

[0003] In the existing technology, few molecular glasses have both phosphorescence and photochromic effects, especially molecular glasses that still have these two effects at room temperature. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide an organic molecular glass with room temperature phosphorescence and photochromism.

[0005] To achieve the above objectives, the present invention provides the following technical solution: An organic molecular glass exhibiting room temperature phosphorescence and photochromism. Includes the following weight parts Phosphorescent guest compound: 1-7 parts Photochromic guest compounds: 1-7 parts Molecular glass main compound: 200~4000 parts.

[0006] As a further improvement of the present invention The molecular glass host compound is BTA, and its molecular formula is: .

[0007] As a further improvement of the present invention The phosphorescent guest compound is at least one of 5,12-dihydroindolo[3,2-A]carbazole, indolo[3,2-B]carbazole, 1,8-naphthalimide, and 1,4,5,8-naphthalenetetracarboxylic diimide.

[0008] As a further improvement of the present invention The photochromic guest compounds are spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], 2,2'-diphenyl-3,3'-biphenylfuran, and cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene.

[0009] As another objective of this invention, a method for preparing an organic molecular glass exhibiting room-temperature phosphorescence and photochromism is provided: Step 1: Take parts by mass of the phosphorescent guest compound, the photochromic guest compound, and the molecular glass host compound; Step 2: Prepare a homogeneous phosphorescent guest solution by mixing the phosphorescent guest compound and the solvent; Step 3: Prepare a homogeneous solution of the photochromic guest compound and solvent; Step 4: Prepare a homogeneous solution of the molecular glass host compound and solvent; Step 5: Mix the homogeneous solution of the phosphorescent guest, the homogeneous solution of the photochromic guest, and the homogeneous solution of the molecular glass host compound to obtain a mixture. Drop the mixture onto a mold and dry it to obtain transparent glass.

[0010] As a further improvement of the present invention In step two, the solvent used is ethanol; In step three, the solvent used is ethanol; In step four, the preparation method involves dissolving the molecular glass host compound in ethanol and heating it.

[0011] As a further improvement of the present invention In step four, the molecular glass host compound is dissolved in ethanol and heated at 60-80°C for 5-8 hours to obtain the product.

[0012] As a further improvement of the present invention In step 5, the drying process involves vacuum drying at 30-50°C for 10-15 hours.

[0013] Molecular glasses have a defined chemical molecular structure, unlike organic polymer films, which are generally composed of fragments. The core of an organic / composite membrane is a polymer substrate plus film-forming / functional additives. These components are strictly avoided in the design of molecular glasses to prevent crystallization and loss of glassy properties. Molecular glasses are amorphous organic small molecules, with a core of organic units possessing a rigid macrostructure and non-planar structure, lacking polymer chains. This is the most fundamental difference in composition and structure between molecular glasses and membranes.

[0014] In this invention, molecular glass is used in combination with phosphorescent guest compounds and photochromic guest compounds. The preferred phosphorescent guest compounds are 5,12-dihydroindolo[3,2-A]carbazole (NA@1), indolo[3,2-B]carbazole (NA@2), 1,8-naphthalimide (NA@3), and 1,4,5,8-naphthalenetetracarboxylic diimide (NA@4). The specific molecular formula of 5,12-dihydroindolo[3,2-A]carbazole (NA@1) is: ; The specific molecular formula of indolo[3,2-B]carbazole (NA@2) is: ; The specific molecular formula of 1,8-naphthalimide (NA@3) is: ; The specific molecular formula of 1,4,5,8-naphthalenetetracarboxylic diimide (NA@4) is: .

[0015] The preferred photochromic guest compounds are spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)] (TNCI), 2,2'-diphenyl-3,3'-biphenylfuran (DBF), and cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE).

[0016] The specific molecular formula of spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)] (TNCI) is: ; The specific molecular formula of 2,2'-diphenyl-3,3'-biphenylfuran (DBF) is: ; The specific molecular formula of cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE) is: .

[0017] BTA is preferred among the molecular glasses, and its specific molecular formula is: .

[0018] The molecular glass prepared by this invention exhibits dual photochromic and phosphorescent properties, and possesses both photochromic and room-temperature phosphorescent optical properties, combining the advantages of both to enhance the material's technological content and added value, and expand high-end application scenarios. Simultaneously, a multi-signal synergistic response mechanism is constructed to ensure its practical application value. Finally, we achieved large-scale industrial preparation of 30 cm × 30 cm doped glass, which still exhibits excellent optical properties.

[0019] It is worth noting that during the preparation process, due to the characteristics of molecular glass, the molecular glass, phosphorescent guest compound, photochromic guest compound and solvent need to be prepared into a homogeneous solution before being mixed. This is to ensure uniform dispersion, as uneven dispersion will inhibit glass formation and prevent the formation of a glassy state. Attached Figure Description

[0020] Figure 1 The HPLC chromatogram of the guest compound 5,12-dihydroindolo[3,2-A]carbazole (NA@1) of this invention is shown. Figure 2 The HPLC chromatogram of the guest compound indo[3,2-B]carbazole (NA@2) of this invention is shown. Figure 3 This is the HPLC chromatogram of the guest compound 1,8-naphthalimide (NA@3) of this invention; Figure 4 This is the HPLC chromatogram of the guest compound 1,4,5,8-naphthalenetetracarboxylic diimide (NA@4) of this invention; Figure 5 These are phosphorescence phenomena diagrams of Examples 1-1, 2-1, 3-1, and 4-1 of the present invention; Figure 6 These are phosphorescence phenomena diagrams of Examples 1-2, 2-2, 3-2, and 4-2 of the present invention; Figure 7 These are phosphorescence phenomena diagrams for Examples 1-3, 2-3, 3-3, and 4-3 of the present invention; Figure 8 The phosphorescence spectra of Examples 1-2, 2-2, 3-2, and 4-2 of this invention are shown below. Figure 9 The phosphorescence spectra of Examples 1-3, 2-3, 3-3, and 4-3 of this invention are shown below. Figure 10 The phosphorescence spectra of Examples 1-3, 2-3, 3-3, and 4-3 of this invention are shown below. Figure 11 This is the NMR spectrum of 2,2'-diphenyl-3,3'-biphenylfuran (DBF) of the present invention. Detailed Implementation

[0021] The present invention will now be described in further detail with reference to the embodiments shown in the accompanying drawings.

[0022] Example 1-1: NA@1 / TNCI / BTA Phosphorescent guest compound NA@1, photochromic guest compound spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)] (TNCI), and host BTA were prepared with a mass ratio of phosphorescent guest compound to host compound of 1:500 and a mass ratio of photochromic guest compound to host compound of 1:500. First, three solutions were prepared: one containing NA@1 dissolved in ethanol at a concentration of 0.1 mmol / L, one containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0023] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of irradiation by the ultraviolet lamp, the apparent color turned blue, and a new absorption peak with a height of 0.21 appeared at 586 nm. After 6 seconds of irradiation by the ultraviolet lamp, the apparent color turned dark blue, and the height of the ultraviolet absorption peak at 586 nm was 0.42. A blue afterglow was observed after 20 seconds of the ultraviolet lamp was removed.

[0024] Examples 1-2: NA@1 / DBF / BTA 5,12-dihydroindolo[3,2-A]carbazole (NA@1), the photochromic guest compound 2,2'-diphenyl-3,3'-biphenylfuran (DBF), and the host BTA glass were prepared with a phosphorescent guest compound to host compound mass ratio of 1:500 and a photochromic guest compound to host compound mass ratio of 1:500. First, three solutions were prepared: one containing NA@1 dissolved in ethanol at a concentration of 0.1 mmol / L, one containing DBF dissolved in ethanol at a concentration of 0.1 mmol / L, and another a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz wafer and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0025] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before irradiation with a 365nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned pink, and a new absorption peak with a height of 0.15 appeared at 560nm. After 6 seconds of UV irradiation, the apparent color remained pink, and the absorption peak at 560nm had a height of 0.50. After the UV lamp was turned off, the material exhibited a blue afterglow for approximately 20 seconds.

[0026] Examples 1-3: NA@1 / DTTE / BTA Phosphorescent guest compound NA@1, photochromic guest compound cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE), and host compound BTA were prepared with a mass ratio of phosphorescent guest compound to host compound of 1:500 and a mass ratio of photochromic guest compound to host compound of 1:500. First, three solutions were prepared: one containing NA@1 dissolved in ethanol at a concentration of 0.1 mmol / L, one containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0027] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of irradiation by the ultraviolet lamp, the apparent color turned red, and a new absorption peak with a height of 0.15 appeared at 590 nm. After 6 seconds of irradiation by the ultraviolet lamp, the apparent color turned deep red, and the height of the ultraviolet absorption peak at 590 nm was 0.4. A blue afterglow was observed after 20 seconds of the ultraviolet lamp was removed.

[0028] Example 2-1: NA@2 / TNCI / BTA Phosphorescent guest compound NA@2, photochromic guest compound spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], and host compound BTA were prepared with a mass ratio of phosphorescent guest compound to host compound of 1:500 and a mass ratio of photochromic guest compound to host compound of 1:500. First, three solutions were prepared: one containing NA@2 dissolved in ethanol at a concentration of 0.1 mmol / L, one containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0029] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of ultraviolet light irradiation, the apparent color turned blue, and a new absorption peak with a height of 0.21 appeared at 600 nm. After 6 seconds of ultraviolet light irradiation, the apparent color turned dark blue, and the height of the ultraviolet absorption peak at 600 nm was 0.41. A green afterglow was observed after 12 seconds of ultraviolet light removal.

[0030] Example 2-2: NA@2 / DBF / BTA Indodo[3,2-B]carbazole (NA@2), the photochromic guest compound 2,2'-diphenyl-3,3'-biphenylfuran (DBF), and the host BTA glass were prepared. The mass ratio of the phosphorescent guest compound to the host compound was 1:500, and the mass ratio of the photochromic guest compound to the host compound was also 1:500. First, three solutions were prepared: one containing NA@2 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing DBF dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0031] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before irradiation with a 365nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned pink, and a new absorption peak with a height of 0.15 appeared at 560nm. After 6 seconds of UV irradiation, the apparent color remained pink, and the absorption peak at 560nm had a height of 0.30. After the UV lamp was turned off, the material exhibited a green afterglow for approximately 12 seconds.

[0032] Examples 2-3: NA@2 / DTTE / BTA Phosphorescent guest compound NA@2, photochromic guest compound cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE), and host compound BTA were prepared at a mass ratio of 1:500 for both the phosphorescent guest compound and the host compound. First, three solutions were prepared: one containing NA@2 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0033] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. After 3 seconds of UV irradiation, the apparent color turned red, and a new absorption peak with a height of 0.15 appeared at 600 nm. After 6 seconds of UV irradiation, the apparent color turned deep red, and the UV absorption peak with a height of 0.4 at 600 nm was observed. A green afterglow was also observed after the UV lamp was removed for 12 seconds.

[0034] Example 3-1: NA@3 / TNCI / BTA Phosphorescent guest compound NA@3, photochromic guest compound spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], and host compound BTA were prepared with a mass ratio of phosphorescent guest compound to host compound of 1:500 and a mass ratio of photochromic guest compound to host compound of 1:500. First, three solutions were prepared: one containing NA@3 dissolved in ethanol at a concentration of 0.1 mmol / L, one containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0035] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of irradiation by the ultraviolet lamp, the apparent color turned blue, and a new absorption peak with a height of 0.23 appeared at 600 nm. After 6 seconds of irradiation by the ultraviolet lamp, the apparent color turned dark blue, and the height of the ultraviolet absorption peak at 600 nm was 0.38. A yellow afterglow was observed 4 seconds after the ultraviolet lamp was removed.

[0036] Example 3-2: NA@3 / DBF / BTA 1,8-Naphthalimide (NA@3), the photochromic guest compound 2,2'-diphenyl-3,3'-biphenylfuran (DBF), and the host BTA glass were prepared with a phosphorescent guest compound to host compound mass ratio of 1:500 and 1:500, respectively. First, three solutions were prepared: one containing NA@3 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing DBF dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz wafer and vacuum-dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed.

[0037] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before irradiation with a 365nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned pink, and a new absorption peak with a height of 0.3 appeared at 560nm. After 6 seconds of UV irradiation, the apparent color remained pink, and the absorption peak at 560nm had a height of 0.50. After the UV lamp was turned off, the material exhibited a yellow afterglow for approximately 4 seconds.

[0038] Example 3-3: NA@3 / DTTE / BTA Phosphorescent guest compound NA@3, photochromic guest compound cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE), and host BTA were prepared at a mass ratio of 1:500 for both the phosphorescent guest compound and the host compound. First, three solutions were prepared: one containing NA@3 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0039] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of irradiation by the ultraviolet lamp, the apparent color turned red, and a new absorption peak with a height of 0.15 appeared at 600 nm. After 6 seconds of irradiation by the ultraviolet lamp, the apparent color turned deep red, and the height of the ultraviolet absorption peak at 600 nm was 0.4. A yellow afterglow was observed after 4 seconds of the ultraviolet lamp was removed.

[0040] Example 4-1: NA@4 / TNCI / BTA Phosphorescent guest compound NA@4, photochromic guest compound spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], and host compound BTA were prepared with a mass ratio of phosphorescent guest compound to host compound of 1:500 and a mass ratio of photochromic guest compound to host compound of 1:500. First, three solutions were prepared: one containing NA@4 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0041] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. After 3 seconds of UV irradiation, the apparent color turned blue, and a new absorption peak with a height of 0.15 appeared at 600 nm. After 6 seconds of UV irradiation, the apparent color turned dark blue, and the UV absorption peak with a height of 0.37 at 600 nm was observed. A red afterglow was also observed after the UV lamp was removed, lasting for 1 second.

[0042] Example 4-2: NA@4 / DBF / BTA 1,4,5,8-Naphthalenetetracarboxydiimide (NA@4), the photochromic guest compound 2,2'-diphenyl-3,3'-biphenylfuran (DBF), and the host BTA glass were prepared with a phosphorescent guest compound to host compound mass ratio of 1:500 and 1:500, respectively. First, three solutions were prepared: one containing NA@4 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing DBF dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz wafer and vacuum dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed.

[0043] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before irradiation with a 365nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned pink, and a new absorption peak with a height of 0.15 appeared at 560nm. After 6 seconds of UV irradiation, the apparent color remained pink, and the absorption peak at 560nm had a height of 0.30. After the UV lamp was turned off, the material exhibited a red afterglow for approximately 1 second.

[0044] Example 4-3: NA@4 / DTTE / BTA Phosphorescent guest compound NA@4, photochromic guest compound cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE), and host BTA were prepared at a mass ratio of 1:500 for both the phosphorescent guest compound and the host compound. First, three solutions were prepared: one containing NA@4 dissolved in ethanol at a concentration of 0.1 mmol / L; another containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L; and the third a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75 °C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40 °C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed. Before being irradiated by a 365nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0045] The ultraviolet-visible absorption spectrum was measured using a Persee TU-1901 instrument. After 3 seconds of irradiation by the ultraviolet lamp, the apparent color turned red, and a new absorption peak with a height of 0.15 appeared at 595 nm. After 6 seconds of irradiation by the ultraviolet lamp, the apparent color turned deep red, and the height of the ultraviolet absorption peak at 595 nm was 0.4. A red afterglow was observed for 1 second after the ultraviolet lamp was removed.

[0046] Comparative Example 1: BTA To obtain BTA, a homogeneous alcoholic solution of BTA was first prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 30 cm × 30 cm quartz wafer and dried under vacuum at 40°C for 12 hours to obtain a transparent glass.

[0047] Comparative Example 2: NA@1 / BTA Guest compound 5,12-dihydroindolo[3,2-A]carbazole (NA@1) and host BTA were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing NA@1 dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed.

[0048] Before being irradiated by a 365 nm ultraviolet lamp, the doped material is transparent and exhibits a blue afterglow for 20 seconds after the ultraviolet lamp is removed.

[0049] No photochromic phenomenon was observed.

[0050] Comparative Example 3: NA@2 / BTA Guest compound indolo[3,2-B]carbazole (NA@2) and host BTA were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing NA@2 dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0051] Before being irradiated by a 365 nm ultraviolet lamp, the doped material is transparent and exhibits a green afterglow for 12 seconds after the ultraviolet lamp is removed.

[0052] No photochromic phenomenon was observed.

[0053] Comparative Example 4: NA@3 / BTA Guest compound 1,8-naphthalimide (NA@3) and host BTA were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing NA@3 dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed.

[0054] Before being irradiated by a 365 nm UV lamp, the doped material is transparent and exhibits a yellow afterglow for 4 seconds after the UV lamp is removed.

[0055] No photochromic phenomenon was observed.

[0056] Comparative Example 5: NA@4 / BTA Guest compound 1,4,5,8-naphthalenetetracarboxydiimide (NA@4) and host BTA were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing NA@4 dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet irradiation were observed.

[0057] Before being irradiated by a 365 nm ultraviolet lamp, the doped material is transparent and displays a red afterglow for 1 second after the ultraviolet lamp is removed.

[0058] No photochromic phenomenon was observed.

[0059] Comparative Example 6: TNCI / BTA Photochromic guest compound spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)] and host BTA glass were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing TNCI dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz crystal and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0060] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before being irradiated with a 365 nm UV lamp, the doped material was transparent. After 3 s of UV irradiation, the apparent color turned blue, and a new absorption peak with a height of 0.33 appeared at 586 nm. After 6 s of UV irradiation, the apparent color turned dark blue, and the height of the UV absorption peak at 586 nm was 0.7.

[0061] No phosphorescence was detected.

[0062] Comparative Example 7: DTTE / BTA A photochromic guest compound, cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene (DTTE), and a host BTA glass were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing DTTE dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz wafer and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0063] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before being irradiated with a 365 nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned blue, and a new absorption peak with a height of 0.28 appeared at 590 nm. After 6 seconds of UV irradiation, the apparent color turned red, and the height of the UV absorption peak at 590 nm was 0.67.

[0064] No phosphorescence was detected.

[0065] Comparative Example 8: DBF / BTA The photochromic guest compound 2,2'-diphenyl-3,3'-biphenylfuran (DBF) and the host BTA glass were prepared at a mass ratio of 1:500. First, two solutions were prepared: one containing DBF dissolved in ethanol at a concentration of 0.1 mmol / L, and the other a homogeneous alcoholic solution of BTA, prepared by dissolving 5 mmol of BTA in 10 mL of distilled ethanol and heating at 75°C for 6 hours. The resulting mixture was then dropped onto a 2 cm × 2 cm quartz wafer and vacuum-dried at 40°C for 12 hours to obtain a transparent glass. The apparent color change and emission color before and after 365 nm ultraviolet light irradiation were observed.

[0066] The UV-Vis absorption spectra were measured using a Persee TU-1901 instrument. Before being irradiated with a 365 nm UV lamp, the doped material was transparent. After 3 seconds of UV irradiation, the apparent color turned pink, and a new absorption peak with a height of 0.30 appeared at 560 nm. After 6 seconds of UV irradiation, the apparent color turned pink again, and the height of the UV absorption peak at 560 nm was 0.59.

[0067] No phosphorescence was detected.

[0068] Detection: 1. The phosphorescent guest compounds 5,12-dihydroindolo[3,2-A]carbazole (NA@1), indolo[3,2-B]carbazole (NA@2), 1,8-naphthalimide (NA@3), and 1,4,5,8-naphthalenetetracarboxylic diimide (NA@4) were monitored by liquid chromatography. Figures 1 to 4 As can be seen, commercially available phosphorescent guest compounds all have high purity and do not require purification.

[0069] 2. The phosphorescence intensity of the examples and comparative examples was tested using a Nanolog FL3-2iHR (Horiba JobinYvon).

[0070] Reference Figure 8 , Figure 9 , Figure 10 As can be seen, all embodiments of the present invention produced phosphorescence with relatively obvious phosphorescence intensity. In contrast, Comparative Examples 6, 7, and 8 did not exhibit phosphorescence.

[0071] 3. Photochromism tests were performed on the examples and comparative examples. The color changes before and after irradiation with a 365 nm ultraviolet lamp for 3 seconds were observed. After that, the ultraviolet lamp was removed and replaced with a white lamp, and the color changes before and after were observed.

[0072] Reference Figure 5 , Figure 6 , Figure 7 It can be observed that the embodiments of the present invention produce a photochromic phenomenon.

[0073] In the above examples and comparative examples, all raw materials except 2,2'-diphenyl-3,3'-biphenylfuran (DBF) were commercially available. The preparation process of 2,2'-diphenyl-3,3'-biphenylfuran (DBF) is as follows:

[0074] Under argon protection, benzofuran-2-boronic acid (200 mg, 1.23 mmol), iodobenzene (126 μL, 1.12 mmol), Pd(OAc)₂ (24 mg, 0.11 mmol), and Na₂CO₃ (237 mg, 2.24 mmol) were placed in a dry Schlenk reactor, along with acetone (6.6 mL) and water (7.7 mL). The reaction mixture was stirred at room temperature, and the reaction was monitored for completion by thin-layer chromatography (TLC) for 8 hours. The reaction mixture was quenched with water and extracted with dichloromethane (3 x 10 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated to dryness under vacuum. The crude product was purified by rapid chromatography (silica gel, pentane / ethyl acetate 98:2) to give 2-phenylbenzofuran.

[0075] A mixture of 2-phenylbenzofuran, 2,3-dicyano-5,6-dichlorobenzoquinone (227 mg, 1 mmol), and dichloroethane (14 mL) was added to a round-bottom flask and stirred at room temperature. The formation of the charge transfer (CT) complex was observed by color change. The mixture was cooled to 0 °C, and methanesulfonic acid (0.4 mL, 6 mmol) was added. After reacting for 5 hours, the reaction mixture was poured into dichloromethane (100 mL), washed three times with water (50 mL), and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel rapid chromatography to obtain compound DBF.

[0076] The obtained DBF was subjected to NMR spectroscopy ((CDCl3, 400 MHz)). Figure 11 As shown, the entire synthesis process has been completed, and compound DBF has been obtained.

[0077] Raw material list:

[0078] The molecular glass prepared by this invention exhibits dual photochromic and phosphorescent properties, and possesses both photochromic and room-temperature phosphorescent optical properties, combining the advantages of both to enhance the material's technological content and added value, and expand high-end application scenarios. Simultaneously, a multi-signal synergistic response mechanism is constructed to ensure its practical application value. Finally, we achieved large-scale industrial preparation of 30 cm × 30 cm doped glass, which still exhibits excellent optical properties.

[0079] The above description is merely a preferred embodiment of the present invention. The scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principles of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. An organic molecular glass exhibiting room temperature phosphorescence and photochromism, characterized in that: Includes the following weight parts Phosphorescent guest compound: 1-7 parts Photochromic guest compounds: 1-7 parts Molecular glass main compound: 200~4000 parts.

2. The organic molecular glass with room temperature phosphorescence and photochromism according to claim 1, characterized in that: The molecular glass host compound is BTA, and its molecular formula is: 。 3. An organic molecular glass with room temperature phosphorescence and photochromism according to claim 1, characterized in that: The phosphorescent guest compound is 5,12-Dihydroindolo[3,2-A]carbazole, Indodo[3,2-B]carbazole, 1,8-Naphthalimide, 1,4,5,8-Naphthalenetetracarboxylic diimide At least one of them.

4. An organic molecular glass with room temperature phosphorescence and photochromism according to claim 1, characterized in that: The photochromic guest compound is Spiro[1,3,3-trimethylindole-(6'-nitrobenzodihydropyran)], 2,2'-Diphenyl-3,3'-Biphenylfuran, cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thiophene)ethylene At least one of them.

5. The method for preparing organic molecular glass according to any one of claims 1 to 4, characterized in that: Step 1: Take parts by mass of the phosphorescent guest compound, the photochromic guest compound, and the molecular glass host compound; Step 2: Prepare a homogeneous phosphorescent guest solution by mixing the phosphorescent guest compound and the solvent; Step 3: Prepare a homogeneous solution of the photochromic guest compound and solvent; Step 4: Prepare a homogeneous solution of the molecular glass host compound and solvent; Step 5: Mix the homogeneous solution of the phosphorescent guest, the homogeneous solution of the photochromic guest, and the homogeneous solution of the molecular glass host compound to obtain a mixture. Drop the mixture onto a mold and dry it to obtain transparent glass.

6. The method for preparing organic molecular glass according to claim 5, characterized in that: In step two, the solvent used is ethanol; In step three, the solvent used is ethanol; In step four, the preparation method involves dissolving the molecular glass host compound in ethanol and heating it.

7. The method for preparing organic molecular glass according to claim 6, characterized in that: In step four, the molecular glass host compound is dissolved in ethanol and heated at 60-80°C for 5-8 hours to obtain the product.

8. The method for preparing organic molecular glass according to claim 5, characterized in that: In step 5, the drying process involves vacuum drying at 30-50°C for 10-15 hours.

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