This PDF file includes:

• Detailed experimental procedures
  
• Materials and methods
  
• Synthetic procedures
  
• X-ray crystallography
  
• Supplementary text
  
• NMR spectra
  
• fig. S1. Sections of the ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectra showing the nonaromatic resonances for biphenylene (top; black), reaction mixture containing two conformers of 14 (middle; blue), and isolated Na₄Mg₂(TMP)₆(1,4-biphenylene-di-ide) 14 (bottom; major conformer).
  
• fig. S2. ¹H,¹H-COSY NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum showing the nonaromatic resonances for the two conformers of 14.
  
• fig. S3. Sections of experimental and simulated ¹H NMR spectra of 14.
  
• fig. S4. Sections of experimental and simulated ¹H NMR spectra of 15.
  
• fig. S5. Molecular structure of 2 showing the contents of the asymmetric unit cell.
  
• fig. S6. Molecular structure of 3 and its extended packing.
  
• fig. S7. Molecular structure of 5 and its extended packing.
  
• fig. S8. Molecular structure of 6 showing atomic connectivity.
  
• fig. S9. Molecular structure of 12 showing the contents of the asymmetric unit cell.
  
• fig. S10. Molecular structure of 13 and its extended packing.
  
• fig. S11. Molecular structure of 14 showing the contents of the asymmetric unit cell.
  
• fig. S12. Molecular structure of 15 and its extended packing.
  
• fig. S13. Molecular structure of 16 showing the contents of the asymmetric unit cell.
  
• fig. S14. ¹H NMR study (400.1 MHz; D₁₂cyclohexane, 300 K) of biphenyl (top; red) and a control reaction of biphenyl and NaTMP in a 1:2 M ratio in methylcyclohexane after 24 hours at 65°C (bottom; blue).
  
• fig. S15. ¹H NMR study (400.1 MHz; D₁₂cyclohexane, 300 K) of biphenyl (top; red) and a control reaction of biphenyl and nBuMgTMP in a 1:2 M ratio in methylcyclohexane after 16 hours at 65°C (bottom; blue).
  
• fig. S16. Representative example of 3,5-dimetalation of biphenyl to give 2.
  
• fig. S17. ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 2.
  
• fig. S18. ¹³C{¹H} NMR (100.6 MHz; D₁₂cyclohexane, 300 K) spectrum of 2.
  
• fig. S19. Sections of the ¹H,¹H-COSY NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 2.
  
• fig. S20. Sections of the phase-sensitive ¹H,¹³C-HSQC NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 2.
  
• fig. S21. Sections of the ¹H,¹³C-HMBC NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 2.
  
• fig. S22. Sections of the ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectra of biphenyl (top; red) and 2 (bottom; blue) showing the aromatic resonances.
  
• fig. S23. Sections of the ¹³C{¹H} NMR (100.6 MHz; D₁₂cyclohexane, 300 K) spectra of biphenyl (top; red) and 2 (bottom; blue) showing the aromatic resonances.
  
• fig. S24. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 3.
  
• fig. S25. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 3.
  
• fig. S26. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 3.
  
• fig. S27. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 3.
  
• fig. S28. ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 3.
  
• fig. S29. ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of an in situ sample of 4.
  
• fig. S30. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 5.
  
• fig. S31. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 5.
  
• fig. S32. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 5.
  
• fig. S33. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 5.
  
• fig. S34. Sections of the ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 5.
  
• fig. S35. ¹H NMR (400.1 MHz; D₁₂cyclohexane/C7H14, 300 K) spectrum of Na₈Mg₄(TMP)12(3,3′,5,5′-para-terphenyl-tetra-ide) 6.
  
• fig. S36. Section of the ¹H,¹H-COSY NMR (400.1 MHz; D₁₂cyclohexane/C₇H₁₄, 300 K) spectrum of Na₈Mg₄(TMP)12(3,3′,5,5′-para-terphenyl-tetra-ide) 6 showing the cross peaks for the aromatic resonances.
  
• fig. S37. Sections of the ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectra of para-terphenyl (top; green), 4 (middle; red), and Na₈Mg₄(TMP)₁₂(3,3′,5,5′-para-terphenyl-tetra-ide) 6 (bottom; blue).
  
• fig. S38. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 7.
  
• fig. S39. ¹³C NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 7.
  
• fig. S40. ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of Na₄Mg₂(TMP)₆(3,5-meta-terphenyl-di-ide) 8.
  
• fig. S41. ¹³C{¹H} NMR (100.6 MHz; D₁₂cyclohexane, 300 K) spectrum of Na₄Mg₂(TMP)₆(3,5-meta-terphenyl-di-ide) 8.
  
• fig. S42. ¹H NMR (400.1 MHz; 300 K, CDCl₃) spectrum of 9.
  
• fig. S43. ¹³C{¹H} NMR (100.6 MHz; 300 K, CDCl₃) spectrum of 9.
  
• fig. S44. ¹H,¹H-COSY NMR (400.1 MHz; 300 K, CDCl₃) spectrum of 3,5-diiodo-meta-terphenyl 9.
  
• fig. S45. ¹H,¹³C-HSQC NMR (400.1 MHz; 300 K, CDCl₃) spectrum of 9.
  
• fig. S46. ¹H,¹³C-HMBC NMR (400.1 MHz; 300 K, CDCl₃) spectrum of 9.
  
• fig. S47. ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of Na₈Mg₄TMP12(3,3′,5,3′-meta-terphenyl-tetra-ide) 10.
  
• fig. S48. Sections of the ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectra of meta-terphenyl (top; green), Na₄Mg₂(TMP)₆(3,5-meta-terphenyl-di-ide) 8 (middle; red), and Na₈Mg₄TMP12(3,3′,5,3′-meta-terphenyl-tetra-ide) 10 (bottom; blue) showing the aromatic resonances.
  
• fig. S49. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 11.
  
• fig. S50. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 11.
  
• fig. S51. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 9.
  
• fig. S52. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 9.
  
• fig. S53. ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 9.
  
• fig. S54. ¹H NMR (400.1 MHz; D₆benzene, 300 K) spectrum of {Na₈Mg₄TMP₁₂3,3″,5,5″-(1′,3′,5′-triphenylbenzene-tetra-ide)} 12.
  
• fig. S55. Section of the ¹H,¹H-COSY NMR (400.1 MHz; D₆benzene, 300 K) spectrum of 12 showing the cross peaks for the aromatic resonances.
  
• fig. S56. ¹H NMR (400.1 MHz; D₆benzene, 300 K) spectra of tpb (top; red) and 12 (bottom; blue).
  
• fig. S57. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 3,3″,5,5″-tetraiodo-5′-phenyl-benzene 13.
  
• fig. S58. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 13.
  
• fig. S59. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 13.
  
• fig. S60. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 13.
  
• fig. S61. ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum sections of 13.
  
• fig. S62. ¹H NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 14.
  
• fig. S63. ¹³C{¹H} NMR (100.6 MHz; D₁₂cyclohexane, 300 K) spectrum of 14.
  
• fig. S64. Sections of the ¹H,¹H-COSY NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 14.
  
• fig. S65. Sections of the phase-sensitive ¹H,¹³C-HSQC NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 14.
  
• fig. S66. Sections of the ¹H,¹³C-HMBC NMR (400.1 MHz; D₁₂cyclohexane, 300 K) spectrum of 14.
  
• fig. S67. ¹³C{¹H} NMR (100.6 MHz; D₁₂cyclohexane, 300 K) section of the spectra of biphenylene (top; red) and isolated 14 (bottom; blue, major conformer).
  
• fig. S68. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 15.
  
• fig. S69. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 15.
  
• fig. S70. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 15.
  
• fig. S71. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 15.
  
• fig. S72. ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 15.
  
• fig. S73. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectra of biphenylene (top; red) and 15 (bottom; blue).
  
• fig. S74. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectra of biphenylene (top; red) and 15 (bottom; blue).
  
• fig. S75. ¹H NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 16.
  
• fig. S76. ¹³C{¹H} NMR (100.6 MHz; CDCl₃, 300 K) spectrum of 16.
  
• fig. S77. ¹H,¹H-COSY NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 16.
  
• fig. S78. ¹H,¹³C-HSQC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 16.
  
• fig. S79. ¹H,¹³C-HMBC NMR (400.1 MHz; CDCl₃, 300 K) spectrum of 16.
  
• table S1. Metalation conditions and scope.
  
• References (53–55, 57–62)

Download PDF