Ever so once in a while, a shonen manga will highlight the romantic relationship between Ichigo and Rukia ^_^. I took the liberty of listing some of these important moments, that are tearful and naming where they appear along with descriptions.

Volume 3: Mother
  Ichigo finds out the truth about his mother, and ends up telling Rukia that he blames himself for her death (showing how much he shares with her). When he has to face the hollow that killed her alone, Rukia insists on helping him but he refuses. Ichigo goes into the fight, while Rukia and Kon take his siblings and family to a safer place, protecting them. Throughout this time, Rukia worries about Ichigo and is distressed, at one point even saying "Don't die Ichigo" tearfully. After a hard fight Ichigo returns to Rukia and she holds him, while rain falls around them xD.

Volume 7: The Broken
  The volume that begins the Soul-Society arc. Byakuya and Renji come to collect Rukia to take her back to Soul-Society because she has broken the rules. While Ishida has failed to save her, Ichigo finds her note and comes to her rescue. Although Ichigo has a good fight against Renji, Byakuya ends his winning streak, slashing him across the chest and leaving him on the floor. Rukia tries to run towards him, saying that he at least deserves to be comforted by her. When Byakuya stops talking, Ichigo holds onto his pant, Byakuya threatens him. Rukia rushes and kicks his hand away, saying that he dare not touch Byakuya, agreeing to go with him to Soul Society, saying to leave Ichigo there since he would die anyways with the present wound. Ichigo looks at her with astonishment, and she tearfully turns her head, telling him not to follow. It is then we know that she did all that to save his life.

Volume 14: Chapter 116 -118
  Ichigo finally reaches Rukia after Byakuya has already wounded the other guy (forgot his name >.>). Rukia, looks at him, suprised to see him comments "Ichigo" (well it was more dramatic than that). When Ichigo goes to her, he tells her he has come to save her, and Rukia tearfully looks at him. He turns to face Byakuya, but Byakuya is about to kill him once more, and Yoruichi saves him and takes him off to train. Ichigo's protection of Rukia was so cute and honorable here ^_^.

Chapter 150-152
  An ultra cute moment of Ichigo and Rukia ^_^. Rukia is about to be executed, and as the bird heads towards her, Rukia says goodbye, only to see Ichigo. He greets her informally, and while she tries to argue with him, he destroys Sokyoku and saves Rukia, telling her that he has come to do just do that. We can hear Rukia's thoughts about Ichigo in this chapter, as she smiles at his strength and he gives her to Renji to get her away from Byakuya and the other captains.

Various Soul Society chapters
  There are other soul society chapters that touch upon the relationship such as Rukia saying goodbye to Ichigo since she wants to stay in Soul Society, Ichigo saving her again, but I can't cover all of them :P

Chapter 195-196
  After an obvious depression since Rukia left him, Ichigo goes back to school, feeling bad about the recent events with Orihime and the new 1/2 hollow & shinigami figures. While he is staying depressed, suddenly some of the soul society people show up, and behind them Ichigo, and he get's a nice reunion with Rukia, obvioulsy much more happy to see her ^_^. Rukia knows just what to say and cheers Ichigo up about him thinking he was too "weak" to protect the people he loves.

Chapter 201
  Ichigo is fighting an arrancar and Rukia comes to save him. This was a really cute moment since the Gigai tells Ichigo that Rukia is really powerful equivalent to a captain's strength, but Byakuya prevented her from becoming a captain to protect her. You can see on the face of Ichigo that he looks sort of jealous of Byakuya and a more like "I can't compete with him look" lol. And of course, Rukia comes and saves him so cutely.

Chapter 235
  Once again in a fight Ichigo has had his armed pinned by GrimmJaw when Rukia comes and tries to save him. She uses her Bankai and freezes Grimmjaw, and sits down next to Ichigo to check if he is okay with a very loving expression. Ichigo is both suprised and sighs in relief until Grimmjaw wakes up and grabs Rukia's face attempting to kill her and Ichigo just stands by and watches has he does so. His expression is both of worry and shock. Of course we all know what happens afterwards.

Chapter 238
  Rukia is taken by Byakuya back to Soul Society and she apologizes to a very sad Ichigo, their departure towards each other is a very nice big panel scene, Rukia leaning out and Ichigo turning his back.

Phew, I know there are many more moments :) but these are just a couple highlights.

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