基于雙卟啉的手性超分子體系及三明治型分子轉(zhuǎn)子體系
發(fā)布時間：2018-09-04 09:15
【摘要】：卟啉是一類典型的剛性共面型共軛大環(huán)分子,具有獨(dú)特的電子結(jié)構(gòu)和光電性能,同時擁有良好的光熱穩(wěn)定性以及易于裁剪修飾等特點(diǎn),使其在化學(xué)、材料及生命科學(xué)等領(lǐng)域具有廣泛的應(yīng)用前景。卟啉類化合物一直是超分子化學(xué)和立體化學(xué)領(lǐng)域的重要研究對象之一。由于卟啉對結(jié)構(gòu)變化、環(huán)境變化及外部刺激具有靈敏的電子和光學(xué)響應(yīng),所以經(jīng)常被作為手性光學(xué)探針單元用于立體選擇性分子識別體系的構(gòu)筑。尤其是共價連接的雙卟啉體系,其中預(yù)置的半剛性空腔不但有利于增強(qiáng)主-客體作用的選擇性,同時使客體誘導(dǎo)的變構(gòu)效應(yīng)表達(dá)為兩個卟啉單元之間的相對位置和取向變化,從而顯著提高(手性)光學(xué)響應(yīng)的靈敏度。另外,三明治型卟啉酞菁類金屬配合物具有獨(dú)特的三維共軛結(jié)構(gòu)體系,其在分子半導(dǎo)體、非線性光學(xué)及分子磁學(xué)領(lǐng)域取得重要進(jìn)展。在此類分子中,“夾心”配位的金屬離子通過多重配位作用連接兩個或多個剛性共軛配體,配體能夠以金屬離子為軸進(jìn)行相對轉(zhuǎn)動,構(gòu)成一類新穎的分子轉(zhuǎn)子體系。本論文主要設(shè)計合成了一系列聯(lián)二萘連接的手性雙卟啉分子,研究其分子內(nèi)手性傳遞、分子間手性調(diào)控現(xiàn)象和對手性二胺的超分子識別作用。另一方面,設(shè)計合成了含有共價鏈連接雙卟啉的三明治型稀土配合物的分子轉(zhuǎn)子,研究了三層配合物分子中處在兩個卟啉環(huán)之間的酞菁環(huán)的相對轉(zhuǎn)動行為;通過配位金屬離子的選擇和連接基團(tuán)的變化對其轉(zhuǎn)動動力學(xué)特性進(jìn)行了調(diào)控。主要研究內(nèi)容如下:1.系列聯(lián)二萘酚橋聯(lián)雙卟啉分子內(nèi)的手性誘導(dǎo)和分子間手性調(diào)控研究了一系列手性雙卟啉主體(H1-H3)的分子內(nèi)手性誘導(dǎo)和分子間手性調(diào)控現(xiàn)象。三對對映異構(gòu)體分別由鋅卟啉和純手性的(R)-或(S)-1,1'-聯(lián)-2-萘酚(BINOL)通過醚鍵或酯基連接構(gòu)成。所有雙卟啉主體的CD光譜都呈現(xiàn)裂分的科頓效應(yīng),而且其CD信號符號與所用BINOL的立體結(jié)構(gòu)一致。從H1到H3,隨著BINOL和卟啉之間連接基團(tuán)的長度和柔性的增加,其CD信號強(qiáng)度逐漸減弱。表明BINOL的手性被表達(dá)為兩個卟啉單元之間的扭轉(zhuǎn)排列,而且這種分子內(nèi)手性誘導(dǎo)效應(yīng)可以通過連接基團(tuán)的長度和剛性進(jìn)行調(diào)控。通過UV-Vis,1HNMR和CD光譜滴定研究了手性雙卟啉主體(H1-H3)與非手性客體(BiPy)及手性客體[(S)-/(R)-DACH]之間的分子間手性調(diào)控現(xiàn)象。光譜滴定結(jié)果表明:1)BiPy和上述三對雙卟啉主體均形成1:1配位的三明治型超分子絡(luò)合物,其CD信號強(qiáng)度都有所減弱,而CD信號符號都沒有變化;2)H1和(S)-/(R)-DACH形成1:2配位的開環(huán)結(jié)構(gòu),CD信號強(qiáng)度減弱而CD符號不變;3)H2和H3與(S)-/(R)-DACH都形成1:1配位的三明治型超分子結(jié)構(gòu),當(dāng)主體與客體同手性時CD信號強(qiáng)度增強(qiáng)而符號不變,當(dāng)主體與客體異手性時CD信號強(qiáng)度增強(qiáng)而且CD符號反轉(zhuǎn)。此外,DFT量子化學(xué)理論模擬得到的優(yōu)化分子構(gòu)型與光譜滴定指認(rèn)的配位模式一致,而且主客體絡(luò)合前后兩個卟啉單元之間距離和扭轉(zhuǎn)角的變化趨勢與其CD光譜的變化趨勢相符合。2.聯(lián)二萘橋聯(lián)的雙卟啉對二胺的手性識別在上一章研究結(jié)果的基礎(chǔ)上,經(jīng)過結(jié)構(gòu)優(yōu)化設(shè)計了一對新的手性雙卟啉主體[(R)-/(S)-H1]用于二胺類客體[(R)-/(S)-DACH,(R)-/(S)-PPDA 和(R)-/(S)-DPEA]的手性識別。UV-Vis,CD和1HNMR光譜滴定表明,(R)-/(S)-DACH和(R)-/(S)-PPDA可以被包夾在該雙卟啉主體的空腔內(nèi),通過雙重Zn-N配位相互作用形成三明治型1:1絡(luò)合物。該絡(luò)合過程對手性二胺的立體構(gòu)型有明顯的CD光譜響應(yīng)。(R)-/(S)-H1的手性識別作用也可以通過NMR滴定的方法檢測到,其中對(R)-/(S)-DACH的不等價化學(xué)位移(△△δ)可以達(dá)到0.57ppm,手性識別能(△△G°)達(dá)到-4.02kJ mol-1。然而由于較大的位阻效應(yīng),另一對手性客體((R)-/(S)-DPEA)不能被包夾在手性雙卟啉的空腔內(nèi)形成三明治型配合物,因此(R)-/(S)-DPEA不能夠被(R)-/(S)-H1識別。研究結(jié)果表明該手性雙卟啉主體同時擁有優(yōu)異的CD和NMR手性識別能力,而且其手性識別能力對配位模式具有依賴性。3.聯(lián)二萘酚橋聯(lián)的手性雙卟啉鈰配合物的合成及性質(zhì)研究合成了三明治性手性雙卟啉鈰配合物(R)-/(S)-1和(R/(S)-2,其中兩個卟啉環(huán)分別通過(R)-(+)-或(S)-(-)-1,1'-二-2-萘酚(BINOL)橋聯(lián)。對(R)-/(S)-1和(R)-/(S)-2進(jìn)行了光譜學(xué)和電化學(xué)表征。對映異構(gòu)體之間呈現(xiàn)相互對稱的CD光譜,在Soret帶(R)-型異構(gòu)體的CD信號為負(fù)而(S)-型異構(gòu)體的CD信號為正;而且(R)-/(S)-1的CD信號強(qiáng)度比(R)-/(S)-2強(qiáng)。結(jié)果表明BINOL基團(tuán)的C2-手性被傳遞到了雙層配合物結(jié)構(gòu),表現(xiàn)為兩個卟啉單元之間具有確定方向的扭轉(zhuǎn)排列,而且其手性傳遞效率可以通過改變連接基團(tuán)的長度進(jìn)行調(diào)節(jié)。4.聯(lián)二萘酚橋聯(lián)的卟啉酞菁混雜三層稀土三明治型分子轉(zhuǎn)子的構(gòu)筑合成了聯(lián)二萘酚連接的混雜卟啉酞菁稀土三明治型配合物(R)-/(S)-1和(R)-/(S)-2作為新型分子轉(zhuǎn)子模型,處于中間的酞菁配體作為轉(zhuǎn)子,而兩側(cè)由BINOL連接的兩個卟啉單元作為定子。通過變溫核磁(VT-NMR)實(shí)驗(yàn)研究酞菁配體的轉(zhuǎn)動行為。通過對VT-NMR譜圖的線型分析得到(R)-1在氘代甲苯和氘代三氯甲烷中的轉(zhuǎn)動能壘分別為57.8 kJmol-1和60.2kJmol-1,(R)-2在氘代甲苯和氘代三氯甲烷中的轉(zhuǎn)動能壘分別為50.0 kJ mol-1和44.1 kJ mol-1。表明通過改變配位的金屬離子可以有效調(diào)控酞菁轉(zhuǎn)子的轉(zhuǎn)動行為。5.偶氮苯橋聯(lián)的光控三明治型分子轉(zhuǎn)子合成了偶氮苯橋連的混雜卟啉酞菁稀土三層三明治型配合物,利用偶氮苯基團(tuán)的可逆光致順-反異構(gòu)性質(zhì),以期實(shí)現(xiàn)對處于分子中間的酞菁配體的轉(zhuǎn)動行為進(jìn)行調(diào)控。用電子吸收光譜和核磁共振光譜對其光致順-反異構(gòu)進(jìn)行了研究,當(dāng)用365 nm波長的光照射20分鐘后,由全反式變?yōu)轫樖秸贾鲗?dǎo)(cis/trans = 76:24)。分別測試了其在反式結(jié)構(gòu)和順式為主時的變溫核磁譜圖,表明反式結(jié)構(gòu)時酞菁環(huán)的轉(zhuǎn)動阻力較大,轉(zhuǎn)速較慢;而順式結(jié)構(gòu)時轉(zhuǎn)動阻力較小,轉(zhuǎn)速較快。該結(jié)果為設(shè)計新型光調(diào)控分子轉(zhuǎn)子提供了基礎(chǔ)。
[Abstract]:Porphyrin is a typical rigid coplanar conjugated macrocyclic molecule with unique electronic structure and photoelectric properties. It has good photothermal stability and is easy to tailor and modify. Porphyrins have a wide range of applications in chemistry, materials and life sciences. Porphyrins have always been supramolecular chemistry and stereochemistry. Porphyrins are often used as chiral optical probe units in the construction of stereoselective molecular recognition systems because of their sensitive electronic and optical responses to structural changes, environmental changes and external stimuli. In addition, sandwich-type porphyrin phthalocyanine metal complexes have unique three-dimensional conjugated structure system, which is in the molecular semi-structure. Important progress has been made in the field of conductors, nonlinear optics and molecular magnetism. In these molecules, sandwich coordination metal ions connect two or more rigid conjugated ligands through multiple coordination interactions, and the ligands can rotate relative to the metal ions on the axis to form a novel class of molecular rotor systems. A series of binaphthalene-linked chiral bisporphyrins were synthesized to study their intramolecular chiral transfer, intermolecular chiral regulation and supramolecular recognition of chiral diamines. On the other hand, a sandwich-type rare earth complex with covalent chain-linked bisporphyrins was designed and synthesized. The relative rotation behavior of the phthalocyanine rings between the porphyrin rings was studied. The kinetics of the rotation was regulated by the choice of coordination metal ions and the change of ligand groups. The main contents are as follows: 1. Chiral induction and chiral regulation of a series of chiral bisporphyrins bridged by binaphthol were studied. Intramolecular chiral induction and intermolecular chiral regulation of (H1-H3). The three enantiomers are composed of zinc porphyrin and pure chiral (R) - or (S) - 1,1'-bi-2-naphthol (BINOL) via ether bonds or ester bonds, respectively. The CD spectra of all bisporphyrin hosts exhibit a split Cotton effect, and their CD signals bind to the stereo of the BINOL used. From H1 to H3, the CD signal intensity decreases with the increase of the length and flexibility of the ligand between BINOL and porphyrin. It shows that the chirality of BINOL is expressed as a torsional arrangement between two porphyrin units, and this intramolecular chiral induction effect can be modulated by the length and rigidity of the ligand. The intermolecular chiral regulation between chiral bisporphyrin host (H1-H3) and non-chiral guest (BiPy) and chiral guest [(S) - / (R) - DACH] was studied by MR and CD spectroscopic titration. The results showed that: 1) BiPy and the above three pairs of bisporphyrin host formed a 1:1 coordination sandwich supramolecular complex, and the CD signal intensity was weakened. Signal symbols remained unchanged; 2) H 1 and (S) - / (R) - DACH formed an open-loop structure with 1:2 coordination, and CD signal intensity weakened while CD symbol remained unchanged; 3) H2 and H3 and (S) - / (R) - DACH formed a sandwich supramolecular structure with 1:1 coordination, and CD signal intensity increased and symbol remained unchanged when the host and the guest were chiral; and CD signal was strong when the host and the guest were heterochromatic. In addition, the optimized molecular configuration simulated by DFT quantum chemical theory is consistent with the coordination pattern identified by spectrophotometric titration, and the variation trend of the distance and twist angle between the two porphyrin units before and after complexation conforms to the variation trend of CD spectrum. 2. Binaphthalene bridged diproporphyrin p-diamine On the basis of the results of the previous chapter, a novel chiral bisporphyrin host [(R) - / (S) - H1] for chiral recognition of diamine guest [(R) - / (S) - DACH, (R) - / (S) - PPDA and (R) - / (S) - DPEA] was designed by structural optimization. UV-Vis, CD and 1H NMR spectroscopic titration showed that, (R) - / (S) - DACH and (R) - / (S) - PPDA could be encapsulated in the bisporphyrin. A sandwich-type 1:1 complex is formed in the cavity of the main body of the porphyrin by double Zn-N coordination interaction. The complex process has obvious CD spectral response to the stereoconfiguration of chiral diamines. (R) - / (S) -H 1 chiral recognition can also be detected by NMR titration, in which the unequal chemical shifts (delta) to (R) - / (S) -DACH can be up to At 0.57 ppm, the chiral recognition energy (delta G degrees) reached - 4.02 kJ mol - 1. However, due to the large steric hindrance effect, the other chiral guest ((R) - / (S) - DPEA) could not be encapsulated in the cavity of chiral bisporphyrins to form sandwich complexes, so (R) - / (S) - DPEA could not be recognized by (R) - / (S) - H1. 3. Synthesis and characterization of chiral bisporphyrin cerium complexes bridged by binaphthol have been studied. Trimeric chiral bisporphyrin cerium complexes (R) - / (S) - 1 and (R / (S) - 2 have been synthesized. Two porphyrin rings pass through (R) - (+) - or (S) - (-) - 1, 1, 1, 2, respectively. '-bis-2-naphthol (BINOL) bridged. Spectroscopic and electrochemical characterizations of (R) - / (S) -1 and (R) - / (S) -2 were carried out. CD spectra of the enantiomers were symmetrical. CD signals of the (R) - type isomers in the Sorret band were negative and that of the (S) - type isomers were positive; and the CD signal intensity ratio of (R) - / (S) - 2 of (R) - / (S) - 1 was strong. C2-chirality is transferred to the double-layer complex structure, which is characterized by the twisted arrangement of two porphyrin units in a definite direction, and the chiral transfer efficiency can be adjusted by changing the length of the linked groups. 4. Binaphthol-bridged porphyrin-phthalocyanine hybrid triple-layer rare earth sandwich molecular rotor is synthesized. Rare earth sandwich complexes (R) - / (S) - 1 and (R) - / (S) - 2 of hybrid porphyrin phthalocyanines are used as new molecular rotor models. The intermediate phthalocyanine ligands are used as the rotor and the two porphyrin units connected by BINOL are used as the stators. The rotational behavior of the ligands is studied by variable temperature nuclear magnetic resonance (VT-NMR). The rotational energy barriers of (R) -1 in deuterated toluene and deuterated trichloromethane were 57.8 kJ mol-1 and 60.2 kJ mol-1, respectively. The rotational energy barriers of (R) -2 in deuterated toluene and deuterated trichloromethane were 50.0 kJ mol-1 and 44.1 kJ mol-1 kJ mol-1, respectively. It was shown that the rotational behavior of phthalocyanine rotors could be effectively controlled by changing the coordination metal ions. Azobenzene-bridged photocontrolled sandwich molecular rotors have been used to synthesize azobenzene-bridged hybrid porphyrin phthalocyanine rare earth triple-layer sandwich complexes. The reversible photoinduced cis-trans isomerization of azobenzene groups has been utilized to modulate the rotation behavior of phthalocyanine ligands in the middle of molecules. Electron absorption spectroscopy and nuclear magnetic resonance spectroscopy have been used. The photoinduced cis-trans isomerization was studied. After irradiation with light of 365 nm wavelength for 20 minutes, it changed from all trans to cis-dominant (cis/trans=76:24). The NMR spectra of trans-and cis-dominant phthalocyanines at different temperatures were measured. The results showed that the rotational resistance of trans-structure was higher and the rotational speed was slower than cis-structure. The resistance is small and the speed is faster. The results provide a basis for designing a new type of light controlled molecular rotor.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2018
【分類號】：O641
本文編號：2221647
[Abstract]:Porphyrin is a typical rigid coplanar conjugated macrocyclic molecule with unique electronic structure and photoelectric properties. It has good photothermal stability and is easy to tailor and modify. Porphyrins have a wide range of applications in chemistry, materials and life sciences. Porphyrins have always been supramolecular chemistry and stereochemistry. Porphyrins are often used as chiral optical probe units in the construction of stereoselective molecular recognition systems because of their sensitive electronic and optical responses to structural changes, environmental changes and external stimuli. In addition, sandwich-type porphyrin phthalocyanine metal complexes have unique three-dimensional conjugated structure system, which is in the molecular semi-structure. Important progress has been made in the field of conductors, nonlinear optics and molecular magnetism. In these molecules, sandwich coordination metal ions connect two or more rigid conjugated ligands through multiple coordination interactions, and the ligands can rotate relative to the metal ions on the axis to form a novel class of molecular rotor systems. A series of binaphthalene-linked chiral bisporphyrins were synthesized to study their intramolecular chiral transfer, intermolecular chiral regulation and supramolecular recognition of chiral diamines. On the other hand, a sandwich-type rare earth complex with covalent chain-linked bisporphyrins was designed and synthesized. The relative rotation behavior of the phthalocyanine rings between the porphyrin rings was studied. The kinetics of the rotation was regulated by the choice of coordination metal ions and the change of ligand groups. The main contents are as follows: 1. Chiral induction and chiral regulation of a series of chiral bisporphyrins bridged by binaphthol were studied. Intramolecular chiral induction and intermolecular chiral regulation of (H1-H3). The three enantiomers are composed of zinc porphyrin and pure chiral (R) - or (S) - 1,1'-bi-2-naphthol (BINOL) via ether bonds or ester bonds, respectively. The CD spectra of all bisporphyrin hosts exhibit a split Cotton effect, and their CD signals bind to the stereo of the BINOL used. From H1 to H3, the CD signal intensity decreases with the increase of the length and flexibility of the ligand between BINOL and porphyrin. It shows that the chirality of BINOL is expressed as a torsional arrangement between two porphyrin units, and this intramolecular chiral induction effect can be modulated by the length and rigidity of the ligand. The intermolecular chiral regulation between chiral bisporphyrin host (H1-H3) and non-chiral guest (BiPy) and chiral guest [(S) - / (R) - DACH] was studied by MR and CD spectroscopic titration. The results showed that: 1) BiPy and the above three pairs of bisporphyrin host formed a 1:1 coordination sandwich supramolecular complex, and the CD signal intensity was weakened. Signal symbols remained unchanged; 2) H 1 and (S) - / (R) - DACH formed an open-loop structure with 1:2 coordination, and CD signal intensity weakened while CD symbol remained unchanged; 3) H2 and H3 and (S) - / (R) - DACH formed a sandwich supramolecular structure with 1:1 coordination, and CD signal intensity increased and symbol remained unchanged when the host and the guest were chiral; and CD signal was strong when the host and the guest were heterochromatic. In addition, the optimized molecular configuration simulated by DFT quantum chemical theory is consistent with the coordination pattern identified by spectrophotometric titration, and the variation trend of the distance and twist angle between the two porphyrin units before and after complexation conforms to the variation trend of CD spectrum. 2. Binaphthalene bridged diproporphyrin p-diamine On the basis of the results of the previous chapter, a novel chiral bisporphyrin host [(R) - / (S) - H1] for chiral recognition of diamine guest [(R) - / (S) - DACH, (R) - / (S) - PPDA and (R) - / (S) - DPEA] was designed by structural optimization. UV-Vis, CD and 1H NMR spectroscopic titration showed that, (R) - / (S) - DACH and (R) - / (S) - PPDA could be encapsulated in the bisporphyrin. A sandwich-type 1:1 complex is formed in the cavity of the main body of the porphyrin by double Zn-N coordination interaction. The complex process has obvious CD spectral response to the stereoconfiguration of chiral diamines. (R) - / (S) -H 1 chiral recognition can also be detected by NMR titration, in which the unequal chemical shifts (delta) to (R) - / (S) -DACH can be up to At 0.57 ppm, the chiral recognition energy (delta G degrees) reached - 4.02 kJ mol - 1. However, due to the large steric hindrance effect, the other chiral guest ((R) - / (S) - DPEA) could not be encapsulated in the cavity of chiral bisporphyrins to form sandwich complexes, so (R) - / (S) - DPEA could not be recognized by (R) - / (S) - H1. 3. Synthesis and characterization of chiral bisporphyrin cerium complexes bridged by binaphthol have been studied. Trimeric chiral bisporphyrin cerium complexes (R) - / (S) - 1 and (R / (S) - 2 have been synthesized. Two porphyrin rings pass through (R) - (+) - or (S) - (-) - 1, 1, 1, 2, respectively. '-bis-2-naphthol (BINOL) bridged. Spectroscopic and electrochemical characterizations of (R) - / (S) -1 and (R) - / (S) -2 were carried out. CD spectra of the enantiomers were symmetrical. CD signals of the (R) - type isomers in the Sorret band were negative and that of the (S) - type isomers were positive; and the CD signal intensity ratio of (R) - / (S) - 2 of (R) - / (S) - 1 was strong. C2-chirality is transferred to the double-layer complex structure, which is characterized by the twisted arrangement of two porphyrin units in a definite direction, and the chiral transfer efficiency can be adjusted by changing the length of the linked groups. 4. Binaphthol-bridged porphyrin-phthalocyanine hybrid triple-layer rare earth sandwich molecular rotor is synthesized. Rare earth sandwich complexes (R) - / (S) - 1 and (R) - / (S) - 2 of hybrid porphyrin phthalocyanines are used as new molecular rotor models. The intermediate phthalocyanine ligands are used as the rotor and the two porphyrin units connected by BINOL are used as the stators. The rotational behavior of the ligands is studied by variable temperature nuclear magnetic resonance (VT-NMR). The rotational energy barriers of (R) -1 in deuterated toluene and deuterated trichloromethane were 57.8 kJ mol-1 and 60.2 kJ mol-1, respectively. The rotational energy barriers of (R) -2 in deuterated toluene and deuterated trichloromethane were 50.0 kJ mol-1 and 44.1 kJ mol-1 kJ mol-1, respectively. It was shown that the rotational behavior of phthalocyanine rotors could be effectively controlled by changing the coordination metal ions. Azobenzene-bridged photocontrolled sandwich molecular rotors have been used to synthesize azobenzene-bridged hybrid porphyrin phthalocyanine rare earth triple-layer sandwich complexes. The reversible photoinduced cis-trans isomerization of azobenzene groups has been utilized to modulate the rotation behavior of phthalocyanine ligands in the middle of molecules. Electron absorption spectroscopy and nuclear magnetic resonance spectroscopy have been used. The photoinduced cis-trans isomerization was studied. After irradiation with light of 365 nm wavelength for 20 minutes, it changed from all trans to cis-dominant (cis/trans=76:24). The NMR spectra of trans-and cis-dominant phthalocyanines at different temperatures were measured. The results showed that the rotational resistance of trans-structure was higher and the rotational speed was slower than cis-structure. The resistance is small and the speed is faster. The results provide a basis for designing a new type of light controlled molecular rotor.
【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2018
【分類號】：O641
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