Nanocrystals of a Metal–Organic Complex Exhibit Remarkably High Conductivity that Increases in a Single-Crystal-to-Single-Crystal Transformation

Abstract

Ag(I) is used to form a π-stacked metal-organic solid that exhibits remarkably high electrical conductivity. The solid undergoes a single-crystal-to-single-crystal [2+2] photodimerization to generate a 1D coordination polymer with over 40% higher conductivity. The Ag(I) complex represents the first example of an increase in conductivity resulting from a [2+2] photodimerization. Density of states calculations show a higher contribution from Ag(I) ions to the valence band in the photodimerized solid, supporting the increase in conductivity.

High conductivity Ag-based metal organic complexes as dopant-free hole-transport materials for perovskite solar cells with high fill factors

“…Obviously, the HA2 -based HTM shows higher hole mobility (8.38 × 10 –4 cm 2 V –1 s –1 ) and conductivity (1.78 × 10 –3 S cm –1 ) than that of the HA1 -based HTM (6.49 × 10 –4 cm 2 V –1 s –1 and 1.05 × 10 3 S cm –1 ), which is ascribed to the introduction of the benzothiadiazole unit expected to enhance the backbone π-coplanarity, resulting in more efficient π–π stacking in HTM films. The results clearly highlight that the two Ag-based HTMs show outstanding conductivity, which can be attributed to the strong face-to-face π–π stacking assisted by Ag···Ag forces, that leads to favorable enhancement of conductivity 43. Notably, the charge-carrier mobility and conductivity of HA1 and HA2 are significantly higher than that of the well-known HTM spiro-OMeTAD (5.31 × 10 –5 cm 2 V –1 s –1 and 8.67 × 10 –5 S cm –1 ),35 indicating that HA1 and HA2 may be suitable candidates as HTMs for PSCs (Fig.…”

Regioselective Photochemical Cycloaddition Reactions of Diolefinic Ligands in Coordination Polymers

“…Anal. Calc'df or C 14 H 12 Isolation of bpbpvcb.Amixture of Na 2 (H 2 edta)·2 H 2 O( 0.372 g, 1mmol), NaOH (0.080 g, 2mmol), H 2 O( 50 mL), CH 2 Cl 2 (50 mL) and 2a (0.239 g, 0.5 mmol) was placed in a1 50 mL flask and stirred for 5h.T he organic phase was separated from the reaction mixture and the aqueous layer was extracted with CH 2 Cl 2 (2 50 mL). The combined organic phase was washed with NaOH solution and H 2 O, and dried with anhydrous Na 2 SO 4 .T he organic phase was concentrated to dryness in vacuo to give tptco as ay ellowish powder.Y ield:0 .085 g( 82 %y ield based on 2a).…”

“…[6][7][8][9][10] Previously,s tudies on such photoreactions in crystalline solids mainlyf ocused on monoolefins. [11][12][13][14] The photocycloaddition reactions based on diolefinic ligands may be more interesting because the neighboring diolefinic molecules can experiencep hotocycloaddition reactions to provide different cyclobutanei somersd epending upon the arrangement of the olefinic bondsp rior to UV irradiation. However,owing to the limited types of diolefins, there are only af ew examples of diolefinsw hich can undergo solid-state[ 2 + +2] photo-polymerization/dimerization in their crystalline state.…”

Features of styryl dye crystal packings and their influence on [2 + 2] photocycloaddition reaction with single crystal retention

“…The PCA reaction is also challenging for creation of information optical recording systems. [3][4][5][6][7]9,[17][18][19][20]22,28,29,38,43,45,46 In studies of PCA reactions it is important to a priori achieve the formation of a "pre-organized" dimeric pair which shows the stacking interaction of the two molecules. 49 However, these reactions are thermal and they proceed in solution.…”

“…8,16 Many reactions of cycloaddition are known in organic chemistry, for instance -[2 + 3] cyloaddition, 47 [3 + 4] cycloaddition, 48 [4 + 2] cycloaddition. Many examples of pre-organized dimeric pairs are described in the literature via the coordination of the initial ethylene systems with metal cations 11,30,32,34,38,40,43,50 or the formation of hydrogen bonds between the components, 7,9,10,12,14,15,17,20,21,[23][24][25]29,30,40,41,46,50 as well as entering two structural units in cavitand cavitycyclodextrins, calixarenes, cucurbit [8]uril, nanocages. Whereas, PCA represents a temperature independent process.…”