Ligand Synthesis. 1,10-Phenanthroline-5,6-dioxime. The reaction was carried out following the slightly modified literature procedure. 5,6-diamino-1,10-phenanthroline. The reduction of 1,10-Phenanthroline-5,6-dioxime was carried out following the slightly modified literature procedure. A mixture of 1,10-Phenanthroline-5,6-dioxime (1.20 g, 5 mmol), Pd/C (0.13 g) and 180 mL of ethanol was purged with nitrogen for 30 minutes and subsequently refluxed under the nitrogen atmosphere for another 30 minutes. Alongside, hydrazine hydrate (N2H4•H2O (50-60%)) (12.1 mL, 149.86 mmol) was also purged with nitrogen for 30 minutes and added dropwise for over a period of 1 hour to the hot solution of 1,10-phenanthroline-5,6-dioxime under the inert atmosphere. The reaction mixture was subsequently refluxed for 24 hours. The hot reaction mixture was filtered through Celite and washed with boiling ethanol. The filtrate was then evaporated under reduced pressure and triturated with 10 mL of water. The mixture was left undisturbed at 4 °C overnight. The formed solid was filtered off, washed with additional water, and dried in the vacuum oven at 40 °C to afford the brown product (597 mg, 2.84 mmol) with 56% yield. The product obtained was used for the subsequent steps without any further purification. H NMR (500 MHz, DMSO-d6): d 8.77 (dd, J = 1.95, 5.2 Hz, 2H), 8.47 (dd, J = 2.0, 10.5 Hz, 2H), 7.6 (m, 2H), 5.21 (s, 4H). [2,3-f] [1,10]phenanthroline (L). In a 100 mL round bottom flask, 200 mg of 5,6-diamino-1,10-phenanthroline (0.95 mmol) and 254 mg (1.2 eq) of 2,2'-Thenil (1.14 mmol) was added and then 15 mL of ethanol with 5 mL of acetic acid were added together. The reaction mixture was stirred for 6 hours at 80 °C and the yellow precipitate formed in the reaction mixture was filtered off and washed with petroleum ether and dried under vacuum at 40 °C to give 278 mg (0.70 mmol) of yellow product with 74% yield. The precipitate obtained was used in the next step without further purification. ). An oven dried, two necked round-bottom flask under a positive pressure of nitrogen was charged with BiCl3 (79.5 mg, 0.25 mmol), ligand (100 mg, 0.25 mmol) and 50 mL anhydrous acetonitrile. The reaction mixture was heated under reflux with constant stirring for 48 hours in nitrogen atmosphere. After the reaction, the resulting faint yellow colored crystalline solid was filtered and washed with diethyl ether and dried in the vacuum oven at 40 C overnight to give 150 mg (0.105 mmol) of product with 41% yield. The complex was used without further purification. The single crystals suitable for structure determination were obtained from slow evaporation of THF. Anal. Calculated for C44H24Bi2Cl6N8S4: H, 1.70; C, 37.12; N, 7.87. Found: H, 1.57; C, 36.92; N, 7.77%. H NMR (600 MHz, DMF-d7):  9.70 (d, J = 2.9 Hz, 4H), 9.61 (d, J = 8.0 Hz, 4H), 8.22 (dd, J = 4.68 Hz, 4H), 7.98 (d, J = 4.0 Hz, 4H), 7.60 (d, J = 3.7 Hz, 4H), 7.26 (t, J = 5.0 Hz, 4H). Due to the weak signals C-NMR could not be collected. ). An oven dried, two necked round-bottom flask under a positive pressure of nitrogen was charged with BiBr3 (84.8 mg, 0.18 mmol), ligand (75 mg, 0.18 mmol) and 50 mL anhydrous acetonitrile. The reaction mixture was heated under reflux with constant stirring for 48 hours in nitrogen atmosphere. After the reaction, the resulting dark yellow colored crystalline solid was filtered and washed with diethyl ether and dried in the vacuum oven Solvothermal synthesis. Bi2Br6(L)2 (2). BiBr3 (56.5 mg, 0.12 mmol), ligand (50 mg, 0.12 mmol) and 20 mL anhydrous acetonitrile were loaded into a 100 mL Teflon-lined stainless-steel autoclave. The autoclave was sealed and heated slowly over 6 hours to 150 °C and then kept at that temperature for 120 hours. The oven was cooled to room temperature (35 °C) over 120 hours.